Compound

ABSTRACT

A compound represented by following formula (I): A-L-{D 1 -(E) q -D 2 -(B) m —Z 1 —R} p . In the formula, A represents a p-valent chain or cyclic residue; L represents a single bond or a divalent linking group; p represents an integer of 2 or more; D 1  represents a carbonyl group (—C(═O)—) or a sulfonyl group (—S(═O) 2 —); D 2  represents a carbonyl group (—C(═O)—), a sulfonyl group (—S(═O) 2 —), a carboxyl group (—C(═O)O—), a sulfonyloxyl group (—S(═O) 2 O—), a carbamoyl group (—C(═O)N(Alk)-) or a sulfamoyl group (—S(═O) 2 N(Alk)-); E represents a divalent group; and R represents a hydrogen atom, a substituted or non-substituted C 8  or longer alkyl group, a perfluoroalkyl group or a trialkylsilyl group.

The present application is a Divisional Application of U.S. applicationSer. No. 12/935,151, filed Sep. 28, 2010, which is the National Stage ofInternational Application No. PCT/JP2009/056367, filed Mar. 27, 2009,and claims foreign priority to Japanese Application Nos. 2008-087957 and2008-087958, filed Mar. 28, 2008, and Japanese Application No.2008-301654, filed Nov. 26, 2008, the entire contents of each of whichare incorporated by reference herein.

TECHNICAL FIELD

The present invention relates to a novel compound. The compound of theinvention is useful for various technical fields inclusive of technicalfields of a lubricant.

BACKGROUND ART

For the purposes of reducing a coefficient of friction and suppressingwear in various friction-sliding places, lubricating oils have been usedin every industrial machine.

In general, current lubricating oils are constituted so as to form afluid film in a sliding gap under a mild friction condition (fluidlubrication condition) and to form a semi-solid coating film at africtional interface under a severe friction condition (boundarylubrication condition). That is, the current lubricating oils contain alow-viscosity oil (namely, a base oil) capable of revealing a lowcoefficient of friction and a chemical which for the purpose ofpreventing direct contact between interfaces to be caused after thelow-viscosity base oil has been broken under a sever friction condition,is able to react with an interface thereof (for example, an ironinterface) to form a tough and soft boundary lubricating film capable ofimparting a low coefficient of friction. Though the chemical isdissolved in the base oil, it is accumulated with time at an interfacethereof due to the reaction with an interface raw material (in general,steel). However, at the same time, the chemical also reacts with themajority of the face which is not directly related to sliding, andaccumulation occurs, whereby the valuable chemical is consumed. Inaddition, even when the chemical is consumed, the base oil does notvanish but actually remains as various decomposition products; and inmany cases, such accelerates deterioration of the lubricating oil perse. Moreover, the boundary lubricating film per se formed by thereaction of the chemical is also peeled off by friction-sliding under asevere condition, and the boundary substrate per se is also peeled off;and they are floated or deposited (sludged) together with the foregoingreaction decomposition products, thereby impairing lubricating abilityof the lubricating oil and causing a factor in deteriorating itsexpected performance. In order to prevent this matter, in general, anantioxidant, a dispersant, a cleaning agent and the like are added to alubricant (Patent Document 1).

In the light of the above, in the majority of current lubricating oils,for the purpose of reducing the friction under an extremely severecondition (boundary lubrication condition) and also the purposes ofreducing and inhibiting side effects of the added chemical, a newchemical is further added. Moreover, for the purpose of reducing alowering of the lubricating function to be caused due to fine wornpowders formed from the interface per se by the wear and decompositionfloats of the chemical, a new chemical is further added. And sincefunctions of various chemicals are related to each other in thelubricating oil, it is inevitable and unavoidable that a period of timewhen the lubricating oil can function as a whole and exhibit the bestlubricating effect becomes short due to exhaustion and deterioration ofthe respective chemicals. It may be said that this is a vicious cycle ofa certain kind. In consequence, it is not easy to greatly improve thecomposition for the purpose of improving performances of currentlubricating oils.

However, all of the foregoing compounds called “chemical” are onescontaining an element reactive with the iron interface, and furthermore,substances formed through a reaction between such a compound and ironhave ability to reduce friction and wear thereof. The element which isessential for the lubrication is phosphorus, sulfur or a halogen andfurthermore, is zinc or molybdenum working competitively andcomplementarily. The former three are distinctly an environmentallyhazardous element, and release thereof into the air even as an exhaustgas must be utterly avoided.

In addition, lubricating oils to be used for internal combustionengines, automatic transmissions and the like are required to be madelow in viscosity for the purpose of achieving fuel saving, and at thesame time, from the viewpoints of effective utilization of resources inrecent years, reduction of waste oil, cost reduction of lubricating oiluser and the like, a requirement for realization of long drain of alubricating oil is increasing more and more. In particular, followinghigh performances of internal combustion engines, high outputs, severedriving conditions and the like, lubricating oils for internalcombustion engine (engine oils) are being required to have higherperformances.

However, in conventional lubricating oils for internal combustionengine, in order to ensure heat or oxidation stability, it is generallyconducted to use a highly refined base oil such as hydrocracked mineraloils, etc., or a high-performance base oil such as synthetic oils, etc.and blend the base oil with a sulfur-containing compound having peroxidedecomposing ability such as zinc dithiophosphate (ZDTP), molybdenumdithiocarbamate (MoDTC), etc., or an ashless antioxidant such as such asphenol based or amine based antioxidants, etc. However, it may not besaid that the heat or oxidation stability by itself is alwayssufficient. Moreover, though it is possible to improve the heat oroxidation stability to some extent by increasing the blending amount ofthe antioxidant, there is naturally a limit in an effect for enhancingthe heat or oxidation stability according to this technique.

And from the viewpoint of an environmental issue such as a reduction ofemission of carbon dioxide, etc., the engine oils are required to bereduced in the content of sulfur or phosphorus for the purposes ofenhancing fuel-saving performance and durability and keeping catalyticability for cleaning an exhaust gas. On the other hand, in dieselengines in recent years, though an emission control mechanism ofparticulate matter, such as a diesel particulate filter (DPF), etc., isstarted to be installed, diesel engine oils are required to realize alow ash from the standpoint of an issue of plugging of the mechanism.The realization of a low ash of engine oils means a reduction of ametallic cleaning agent, and it is an extremely important problem toensure diesel engine cleaning properties to be kept by blending a largeamount of a metallic cleaning agent or an ashless dispersant, inparticular, cleaning properties of a top ring groove with a high heatload.

When an internal combustion engine is taken as an example, the foregoinglubrication is concerned with lubrication of portions other than acombustion chamber and a lubricating composition. However, as for thelubrication of the combustion chamber, there is actually a big problem,too. That is, studies for controlling (preventing or decreasing) areduction of deposits formed in a fuel introducing port of thecombustion chamber, or a reduction of friction and wear to be causedthereby, by trace additives to be added to the fuel have been continuedover a period of many years.

In particular, in recent years, from the viewpoint of exhaust gasregulation, it has been becoming essential to realize a low sulfurconcentration of a fuel composition. However, there is a concern thataccording to this, the lubricating properties are lowered, therebycausing a lowering of durability of a valve gear mechanism includingcams and valves. Here, it is also driven by necessity to review theconventional element contributing to a reduction of friction and wear.

That is, in order to exhibit efficacy by small amount addition,reactivity with an interface raw material is an essential requirement,and nevertheless an element capable of revealing desired low friction byforming a boundary lubricating film is essential, at the same time, itis required to reduce sulfur, phosphorus and heavy metals, the presenceper se of which is problematic. The lubricating oils are a materialsupporting the current industrial machines themselves, and even if theyare not easily displaced, this is the moment at which a composition oflubricating oil and a lubrication mechanism per se as a backgroundthereof must be seriously reviewed by the latest scientific technologiesand functional raw material technologies after a lapse of 150 years ormore.

At the beginning, while it has been described that “For the purposes ofreducing a coefficient of friction and suppressing wear in variousfriction-sliding places, lubricating oils have been used in everyindustrial machine”, a mission of the lubricating oil itself is to keepand preserve a motor function of machine. Though we make a machine workand utilize it, when the work (action) is taken out (counteraction),friction is inevitably caused at a mutually sliding interface. In orderto reduce vigorous wear generated by the friction and prevent amechanical damage such as seizure, etc. from occurring, it is necessaryto ensure a sliding gap, and for that reason, various solid or liquidlubricating films have been applied.

A theoretical analysis of the behavior of such a liquid film in thefriction state starts from the matter that the Navier-Stokes equationsdescribing the motion of a viscous fluid in the hydrodynamics wereapplied to a gap with a narrow Reynolds. In those days, anexperimentally verified phenomenon in which a wedge-shaped oil film in abearing generates a high hydrodynamic pressure was theoreticallyexplained, thereby laying the foundation of the fluid lubrication theoryof the day.

According to this theory, in view of the fact that the Sommerfeld numberwhich is utilized as a basic characteristic number of the bearing designis expressed by the following equation, it is noted that a filmthickness d of a sliding gap is related to a pressure P, a viscosity η(→ also correlated with a temperature T) and a sliding velocity V. Sincethe film thickness d itself of the sliding gap accurately depends uponan average roughness Ra of the surface thereof, it may be said thatfactors relating to breakage of the film thickness d of the sliding gapare the pressure P, the temperature T, the viscosity η, the averageroughness Ra of the surface and the sliding velocity V.

Sommerfeld number S=[η(T)*R(bearingradius)*V(velocity)]/[2πP(pressure)*d ²(gap)]

From the viewpoint of keeping the oil film, as for the factorsinfluencing the gap d, it may be easily analogized that at a hightemperature, factors of a reduction of the viscosity of the oil film andan interface roughness are important and that under a high pressure, thepressure and the pressure dependency of the oil film viscosity arenaturally important.

In consequence, the history of a technology for keeping a liquid filmstarted from control of the viscosity of a base oil. First of all, inorder to prevent breakage, an oil with relatively high viscosity, namelya highly viscous oil is used. However, a machine must start up, and atthat time, a high viscosity is disadvantageous. Furthermore, in general,at the start-up time, the temperature is lower than that at theoperation time, in most cases, the oil hardly moves because of itsextremely high viscosity; and therefore, in a sense of utterly avoidingbreakage at the high-temperature time, a high viscosity index oil whichis originally low in viscosity was used, and furthermore, a polymer(viscosity index improver) was added to a low-viscosity base oil.

The technology developed in response to severer conditions at a hightemperature and under a high pressure is a technology concerning aninterface protective film (boundary lubricating film) capable of firmlyadhering directly to an interface, in particular an iron interface andhaving flexibility. Historically, starting from the addition of a soap,inorganic films such as iron chloride, iron sulfide, iron phosphate,etc. were formed; and in recent years, reactive and low-frictionorganometallic complexes such as Mo-DTC, Zn-DTP, etc. have beendeveloped, and a trace amount thereof is added to a base oil.

Though there were an improvement of viscosity physical propertiesagainst the temperature as described previously and a technicaldevelopment of forming a lubricating film by another method, a technicaland simple approach as in the invention, in which a viscosity-pressuremodulus is controlled and optimized for the purpose of inhibitingbreakage of an oil film while controlling the viscosity against thepressure has not been revealed yet.

However, the theory concerning the viscosity-pressure modulus has beensurely established with the times.

As for the friction mechanism, there is known an elastic fluidlubrication mechanism between the foregoing mild fluid lubricationmechanism and severe boundary lubrication mechanism. A theoretical studyof this elastic fluid lubrication mechanism started from the studyregarding the true contact face shape and the generated pressure,published by Hertz in 1882; established by a summary of the EHL elasticfluid lubrication theory by Petrosevich in 1951; and became a practicaltheory by an oil film formation theory taking into consideration ofelastic deformation by Dowson/Higginson in 1968.

A region where this elastic fluid lubrication mechanism works is afriction region under a high pressure of, for example, several tons percm², namely about several hundred MPa. At a glance, though such acondition is severe, in fact, since iron starts to cause elasticdeformation within such a pressure range, the area of the true contactface of the iron interface coming into contact with the oil filmincreases, and the substantial pressure becomes low. That is, withinthis region, so far as an elastic limit of iron or oil film breakage isnot caused, the coefficient of friction does not increases, and it maybe said that such a region is a “blessed region” for the slidinginterface. Moreover, at the same time, in this region, an oil film madeof a general lubricating oil such as mineral oils becomes high inviscosity by about 1,000 times that at the time of atmospheric pressure,but there may be the case where it becomes low in viscosity by onlyabout 500 times depending upon a chemical structure of the raw material.Barus expressed this phenomenon relative to pressure dependency of theviscosity of liquid in terms of the following equation (VII) andexhibited that an increase rate α of viscosity which is inherent in thesubstance to pressure is related (Non-Patent Document 1).

η=η₀ exp(αP)  (VII)

Here, α represents a viscosity-pressure modulus; and η₀ represents aviscosity at atmospheric pressure.

Moreover, Doolittle advocated a thought of a free volume model that aviscosity of liquid is determined by a ratio of an occupied volume ofmolecule occupied in a liquid volume and a free volume generated bythermal expansion (Non-Patent Document 2).

η=Aexp(BV ₀ /V _(f))  (VIII)

Here, η represents a viscosity; V₀ represents an occupied volume ofmolecule; and V_(f) represents a free volume.

In comparison between the equation (VIII) of Doolittle and the equation(VII) of Barus, it is noted that the viscosity-pressure modulus α is ininverse proportion to the free volume of molecule. That is, what theviscosity-pressure modulus is small suggests that the free volume ofmolecule is large. In consequence, it is noted that it is possible tocontrol the pressure dependency of the viscosity of liquid by optimizinga chemical structure of raw material, namely, it is possible to providea raw material having a lower viscosity than oils constituting currentlubricating oils under the same high-load and high-pressure conditionsby optimizing the chemical structure. For example, assuming that an oilfilm of a true contact part is formed by a raw material having aviscosity-pressure modulus α of about a half of that of mineral oils orhydrocarbon based chemical synthetic oils such as poly-α-olefins, whichare usually used as a lubricating oil, this elastic fluid lubricationregion is laid under a milder condition. That is, in usual lubricatingoils, even under a high load which is classified into the boundarylubrication region, in view of the fact that a cooling effect by an oilfilm as well as low pressure and low viscosity of the true contact siteis added due to the elastic deformation of the interface and thelow-viscosity oil film under a high pressure, it is expected tosubstantially avoid the boundary lubrication region and realize an ideallubrication mechanism made of only fluid lubrication.

In recent years, it is disclosed that discotic compounds having aplurality of radially arranged relatively long carbon chains andlubricating oils containing the same (namely, a metallic rawmaterial-free lubricating oil) exhibit a low coefficient of friction inthe elastic fluid lubrication region (for example, Patent Documents 2 to4). Such a discotic compound has a discotic core and side chainsradially extending from the discotic core, and it is expected that asector-shaped free volume can be inevitably ensured in a highly arrangedstate, too. In consequence, discotic or tabular compounds havingradially arranged side chains have many free volumes in common ascompared with an occupied volume thereof, and therefore, they exhibit asmall viscosity-pressure modulus. That is, it is expected that theviscosity is relatively small even under a high pressure, and lowerviscosity and lower friction properties are revealed under a highpressure (Non-Patent Document 3).

However, what is common among these raw materials is the matter that theviscosity thereof is larger by one digit than that of mineral oils andchemical synthetic oils usually used for lubricating oils, and it isabsolutely impossible to use a large amount of such a raw materialinexpensively in place of low-viscosity base oils.

That is, though the viscosity under a high pressure is defined by theviscosity η₀ and the viscosity-pressure modulus α as expressed by theforegoing equation (VII), when a low-viscosity base oil is actuallyused, it already starts to be broken in an elastic fluid lubricationregion, and it becomes in a viscosity-free state, namely anelasto-plastic body under a high pressure. It has been elucidated thateasiness of breakage of this lubricating oil film is correlated with anagglomerated state of fluid molecules, namely a packing state oflubricating oil molecules and can be evaluated by a product αP of theviscosity-pressure modulus α and the pressure P (Non-patent Document 4).

In general, the lubricating oil film acts as a viscous fluid when theproduct αP is not more than 13, as a visco-elastic fluid when theproduct αP is between 13 and 25 and as an elasto-plastic body when theproduct αP is 25 or more, respectively. In the case where two kinds oflubricating oil films having the same viscosity η under a certainpressure P, where a viscosity-pressure modulus is defined as α₁ and α₂,respectively, and also a normal pressure viscosity is defined as η₁ andη₂, respectively, the following equation is established.

ln η=ln η₁+α₁ ·P=ln η₂+α₂ ·P

In the case of 18=α₁·P<α₂·P=24, namely α₁/α₂=18/24, it is noted thatwhen the pressure P is increased a little more, the film having aviscosity-pressure modulus α₂ becomes an elasto-plastic body and is moreeasily broken even under the same pressure at the same viscosity.

In consequence, even when a base oil having a relatively large η₀ tosuch extent that it can be used even in a fluid lubrication region isutilized, since the viscosity-pressure modulus α of an chain hydrocarbonsuch as mineral oils constituting a base oil is large, there iseventually a tendency that the viscosity η under a high pressure becomeslarge, and it has been considered that neither base oil having avisco-elastic fluid region nor organic compound, each of which has a lowη₀ capable of imparting a low coefficient of friction under fluidlubrication and a low α capable of imparting a low coefficient offriction under elastic fluid lubrication at the same time, is present sofar.

For the time being, even if a raw material capable of clearing theforegoing restrictions could be developed, taking into considerationnecessary conditions of base oils requiring large-amount feed and lowcosts, it is difficult to provide a raw material satisfying all of them.Therefore, as for engine oils which are essential to be low in viscosityfor the purpose of achieving low fuel consumption, it may be consideredthat there is a background wherein a concept itself for effectivelyutilizing elastic fluid lubrication was not recognized. It may be saidthat convergence of the raw material development to a combination of acurrent low-viscosity based oil and a trace chemical capable of forminga boundary lubricating film as described at the beginning was aninevitable result.

-   [Patent Document 1] JP-T-2005-516110-   [Patent Document 2] JP-A-2006-328127-   [Patent Document 3] JP-A-2007-92055-   [Patent Document 4] JP-A-2006-257383-   [Non-Patent Document 1] C. Barus, Am. J. Sci., 45 (1893), page 87-   [Non-Patent Document 2] A. K. Doolittle, J. Appl. Phys., 22 (1951),    1471-   [Non-Patent Document 3] Masanori HAMAGUCHI, Nobuyoshi OHNO, Kenji    TATEISHI and Ken KAWATA, Preprint of the International Tribology    Conference (Tokyo, 2005-11), page 175-   [Non-Patent Document 4] Nobuyoshi OHNO, Noriyuki KUWANO and Fujio    HIRANO, Junkatsu (Lubrication), 33, 12 (1988), 922; 929

DISCLOSURE OF THE INVENTION Problems to be Resolved by the Invention

One object of the invention is to provide a novel compound which isuseful in various fields inclusive of technical fields of a lubricant,etc.

Means of Solving the Problems

The means for achieving the objects are as follows.

[1] A compound represented by following formula (Z):

A-L-{D¹-(E)_(q)-D²-(B)_(m)—Z¹—R}_(p)  (Z)

wherein

A represents a p-valent chain or cyclic residue;

L represents a single bond, an oxy group, a substituted ornon-substituted oxymethylene group represented by following formula(A-a), or a substituted or nonsubstituted oxyethyleneoxy grouprepresented by following formula (A-b):

—(O—C(Alk)₂)-  (A-a)

—(O—C(Alk)₂C(Alk)₂O)—  (A-b)

Alk represents a hydrogen atom, a C₁-C₆ alkyl group or a cycloalkylgroup;

p represents an integer of 2 or more;

D¹ represents a carbonyl group (—C(═O)—) or a sulfonyl group (—S(═O)₂—),and each D¹ may be the same as or different from every other D¹;

D² represents a carbonyl group (—C(═O)—), a sulfonyl group (—S(═O)₂—), acarboxyl group (—C(═O)O—), a sulfonyloxyl group (—S(═O)₂O—), a carbamoylgroup (—C(═O)N(Alk)-) or a sulfamoyl group (—S(αO)₂N(Alk)-), and each D²may be the same as or different from every other D², wherein Alkrepresents a hydrogen atom, a C₁-C₆ alkyl group or a cycloalkyl group;

E represents a substituted or nonsubstituted alkylene group,cycloalkylene group, alkenylene group, alkynylene group or arylenegroup, a divalent heterocyclic aromatic ring group or heterocyclicnon-aromatic ring group, a divalent group selected among an imino group,an alkylimino group, an oxy group, a sulfide group, a sulfenyl group, asulfonyl group, a phosphoryl group and an alkyl-substituted silyl group,or a divalent group composed of a combination of two or more of thesegroups; q represents an integer of 0 or more; and when q is 2 or more,each E may be the same as or different from every other E;

R represents a hydrogen atom, a substituted or non-substituted C₈ orlonger alkyl group, a perfluoroalkyl group or a trialkylsilyl group, andeach R may be the same as or different from every other R;

B varies depending upon R;

in the case where R represents a hydrogen atom or a substituted ornon-substituted C₈ or longer alkyl group, B represents a substituted ornon-substituted oxyethylene group or a substituted or non-substitutedoxypropylene group; plural Bs connecting to each other may be the sameas or different from each other; and m represents a natural number of 1or more;

in the case where R represents a perfluoroalkyl group, B represents anoxyperfluoromethylene group, an oxyperfluoroethylene group or anoptionally branched oxyperfluoropropylene group; plural Bs connecting toeach other may be the same as or different from each other; and mrepresents a natural number of 1 or more;

in the case where R represents a trialkylsilyl group, B represents adialkylsiloxy group in which the alkyl group is selected among a methylgroup, an ethyl group and an optionally branched propyl group; each Bmay be the same as or different from every other B; plural Bs connectingto each other may be the same as or different from each other; and mrepresents a natural number of 1 or more; and

Z¹ represents a single bond, a divalent group selected among a carbonylgroup, a sulfonyl group, a phosphoryl group, an oxy group, a substitutedor non-substituted amino group, a sulfide group, an alkenylene group, analkynylene group and an arylene group or a divalent group composed of acombination of two or more of these groups.

[2] The compound according to [1], wherein in the formula (Z), A is aresidue of pentaerythritol, glycerol, oligo-pentaerythritol, xylitol,sorbitol, inositol, trimethylolpropane, ditrimethylpropane, neopentylglycol or polyglycerin.

[3] The compound according to [1], wherein in formula (Z), A is a grouprepresented by any of following formulae (AI) to (AIII):

wherein

* means a bonding site to -L-D¹-(E)_(q)-D²-(B)_(m)—Z¹—R; C represents acarbon atom; R⁰ represents a hydrogen atom or a substituent; each of X¹to X⁴, X¹¹ to X¹⁴ and X²¹ to X²⁴ represents a hydrogen atom or a halogenatom and may be the same as or different from every other; each of n1 ton3 represents an integer of from 0 to 5; and m4 represents an integer offrom 0 to 2.

[4] The compound according to any one of [1]-[3], wherein in the formula(Z), each —(B)_(m)—Z¹—R is a group represented by following formula(ECa), and each —(B)_(m)—Z¹—R may be the same as or different from everyother —(B)_(m)—Z¹—R:

wherein

in the formula (ECa), C represents a carbon atom; O represents an oxygenatom; R^(a) corresponding to R in the formula (Z) represents asubstituted or non-substituted C₈ or longer alkyl group; L^(a)corresponding to Z¹ in the formula (Z) represents a single bond or adivalent connecting group; each of X^(a1) and X^(a2) represents ahydrogen atom or a halogen atom; na1 represents an integer of from 1 to4; when na1 is 2 or more, plural X^(a1)s and X^(a2)s may be the same asor different from each other; and na2 represents a number of from 1 to35.

[5] The compound according to [4], wherein in formula (Z), L^(a)corresponding to Z¹ is a single bond or a divalent connecting groupcomposed of a combination of one or more members selected among acarbonyl group, a sulfonyl group, a phosphoryl group, an oxy group, asubstituted or non-substituted amino group, a thio group, an alkylenegroup, an alkenylene group, an alkynylene group and an arylene group.

[6] The compound according to any one of [1]-[3], wherein in formula(Z), each —(B)_(m)—Z¹—R is a group represented by following formula(ECb), and each —(B)_(m)—Z¹—R may be the same as or different from everyother —(B)_(m)—Z¹—R:

wherein

in the formula (ECb), the same symbols as those in the formula (ECa)according to [4] are synonymous, respectively; L^(a1) corresponding toZ¹ in the formula (Z) represents a single bond; na2 represents a numberof from 0 to 2; nc represents a number of from 1 to 10; m represents anumber of from 1 to 12; and n represents a number of from 1 to 3.

[7] The compound according to any one of [1]-[3], wherein in formula(Z), each —(B)_(m)—Z¹—R is a group represented by following formula(ECc), and each —(B)_(m)—Z¹—R may be the same as or different from everyother —(B)_(m)—Z¹—R:

wherein

in formula (ECc), the same symbols as those in formula (ECa) accordingto [4] are synonymous, respectively; each Alk′ may be the same as ordifferent from every other Alk′ and represents a C₁-C₄ alkyl group;L^(a1) corresponding to Z¹ in the formula (Z) represents a single bond;and nb represents a number of from 1 to 10.

Effect of the Invention

According to the invention, it is possible to provide a novel compoundwhich is useful in various fields inclusive of technical fields of alubricant, etc.

MODE FOR CARRYING OUT THE INVENTION

The invention is described in detail hereinunder. Note that, in thisdescription, any numerical expressions in a style of “ . . . to . . . ”will be used to indicate a range including the lower and upper limitsrepresented by the numerals given before and after “to”, respectively.

1. Compound Represented by Formula (Z)

A-L-{D¹-(E)_(q)-D²-(B)_(m)—Z¹—R}_(p)  (Z)

In the formula, A represents a p-valent chain or cyclic residue.

A preferred example of A is a residue containing a branched structure inwhich atoms within the third (γ-position) from the atom (α-position) inA bonding to -L are secondary or more. The compound represented by theformula (Z) containing such A belongs to a compound group expressed as aso-called “starburst shape” or “star shape”, and exhibits preferrednatures as a lubricant composition or the like.

The compound “having a small increase rate of viscosity by pressure” asdescribed previously is useful in a technical field of lubricant, and itis also described previously that Non-Patent Document 2 discloses thatsuch a nature can be achieved by a compound “having a large free volumeas far as possible”. An example of the compound “having a large freevolume as far as possible” is a compound in which the free volume ofplural side chains present in the molecule is large.

When a triphenylene compound is taken as an example for the compoundhaving a discotic structure, for example, in a triphenylene havinglong-chain alkoxy groups at 2-, 3-, 6-, 7-, 10- and 11-positions, sidechains composed of such a long-chain alkoxy group naturally extendradially, and the farther the side chain is from the center startingfrom the oxygen atom in the alkoxy group, the larger the volume of aspace where the side chain can freely move (free volume) is. Even whenthe subject compound is accumulated in a high density, or it takes ahexagonal closest packing structure of a columnar structure such as aliquid crystal phase or a crystal, a minimal space where the side chaincan take a certain movement. This is a significant difference between adiscotic molecule and a string-like molecule. When the string-likemolecule is uniaxially oriented, the free volume is lost.

Next, a molecule having a structure in which side chains extend equallyin four directions against the space centering an SP3 element in exactlya “starburst shape” or “star shape” as in methane, tetramethylsilane,trimethylamine, etc. is considered. In such a molecule, it may beconsidered that similar to the molecule having a discotic structure, itis theoretically possible to similarly ensure its free volume; however,the actual situation is considerably different. In the discotic moleculeas described previously, a discotic nucleus itself ensures a space wherea side chain can freely move until a distance of a certain degree fromits center, from the first due to an incorruptible nucleus structurethereof, whereas in the “starburst-shaped” or “star-shaped” molecule, astructure in which carbon chains are extended centering the SP3 elementdirectly from this element is taken; and therefore, there is asignificant difference therebetween.

For example, in comparison between the position of oxygen of ahexaalkoxytriphenylene as the foregoing discotic compound and theposition of oxygen of triethoxylate of trimethylolmethane as the“starburst-shaped” or star-shaped” compound, as schematically below,when approximated in terms of a length of the chain of SP3 carbon, theposition of oxygen is corresponding to the position of carbon fromapproximately the fourth from SP3 carbon of the central nucleus, namelycarbon of the epoxy group terminal. At a glance, the latter has a higherdegree of freedom; however, when the density increases, and themolecules start to agglomerate, other side chain also comes into a spacein the vicinity of each of the side chains, the respective side chainsare bent, or the side chains become approximately in a rod-like shape insuch a manner of closing an umbrella, thereby possibly reducing the freevolume. It may be easily supposed that when the density is actuallyincreased, the state of the side chains will change in such a way.

Even in molecules having a nucleus of a non-discotic structure, such assuch an SP3 element-containing nucleus, etc., for the purpose ofenabling a side chain thereof to ensure a large space volume similar toa side chain of a discotic molecule, the present inventor made extensiveand intensive investigations on what structure of the side chain issuitable. As a result, the invention has been accomplished on the basisof the resulting knowledge.

Though the following acetoxytrimethylolmethane is one obtained byconverting the triethoxylate of trimethylolmethane into an ester, thisstructure is a basic structure of fat and oil in the world oflubrication. The fat and oil as referred to herein is a polyol ester ofa fatty acid and has a structure in which a lower viscosity-pressuremodulus, namely a lower coefficient of friction under a high pressurethan that of a mineral oil can be easily revealed.

It may be presumed that reasons for this reside in the facts that therotational barrier energy of C—O in the ester is smaller than that ofC—C; and that since electron repulsion and steric repulsion betweencarbonyl groups are easy to open radially, the free volume can belargely ensured. Certainly, an ester of a polyol tends to be low infriction as compared with an ester of a polycarboxylic acid. It may beconsidered that this is related to the size of the free volumeinfluencing the whole of side chains of the rotation of C—O.

But, current ester oils are low in friction as compared with mineraloils, a degree of which is, however, not conspicuous so much. Then, thepresent inventor has made extensive and intensive investigationsregarding a lubricating effect of a compound having a carbonyl group inthe tip of a further extended side chain and found that the followingcompound obtained by linking a residue corresponding to succinic acid totrimethylolmethane exhibits a conspicuous friction reducing effect.

This result is revealed in not only a 1,4-dicarbonyl group as insuccinic acid but a 1,3-dicarbonyl group, a 1,5-dicarbonyl groupinterposing oxygen in a center thereof, etc. Moreover, a polyol ester ofacylated sarcosinic acid also reveals the same friction reducing effect.

In consequence, the invention is concerned with a compound having achain or cyclic chemical structure capable of radially arranging sidechains and having radially extending side chains linked thereto, and itutilizes a compound capable of ensuring a larger free volume. In orderthat the side chains may ensure a large free volume, it is preferable tohave a chemical structure designed such that the side chains are easy tofreely rotate in the vicinity of a bonding site to a central nucleus andthat the side chains cause repulsion each other. In this specification,the compound having the thus designed side chains is collectivelyexpressed as a “starburst-shaped” or “star-shaped” compound.

While the compound having a central nucleus containing an SP3 carbonelement and containing a branched structure formed thereby has beendescribed, the structure of the central nucleus is not particularlylimited so far as the side chains are able to ensure a large freevolume. As a matter of course, the structure may be a cyclic structure.Moreover, in a compound obtained by connecting a side chain having aprescribed structure (-D¹-(E)_(q)-D²-(B)_(m)—Z¹—R) which the compoundrepresented by the foregoing formula (Z) has, to a central nucleuscontaining an element capable of becoming trivalent or polyvalent, suchas nitrogen, silicon, boron, phosphorus, etc. and containing a branchedstructure formed thereby, the side chain is also able to ensure a largefree volume and exhibits the same effect; and such compounds fall withinthe scope of the invention.

Moreover, the compound of the invention may be either a polymer or anoligomer. More specifically, in a polymer or oligomer obtained byconnecting the side chain having a prescribed structure(-D¹-(E)_(q)-D²-(B)_(m)—Z¹—R) to a side chain of one or two or morekinds of repeating units constituting a principal chain thereof, and theside chain is also able to ensure a large free volume and exhibits thesame effect. The principal chain of the polymer or oligomer may be, forexample, a simple structure as in a polyvinyl alcohol chain.Specifically, a polymer or oligomer obtained by substituting an acetylgroup of polyvinyl acetate with the side chain having a prescribedstructure (-D¹-(E)_(q)-D²-(B)_(m)—Z¹—R), which the compound representedby the foregoing formula (Z) has, falls within the scope of theinvention.

Among examples of the central nucleus structure bonding the foregoingside chain thereto, those of hydrocarbon chains include pentaerythritol,oligo-pentaerythritols inclusive of di-, tri- or tetraerythritol, groupsobtained by connecting one hydroxyl group of pentaerythritol to otherdivalent group (for example, a substituted or non-substituted alkylenegroup, cycloalkylene group, alkenylene group, alkynylene group orarylene group, a divalent heterocyclic aromatic ring group orheterocyclic non-aromatic ring group, a divalent group selected among animino group, an oxy group, a sulfide group, a sulfenyl group, a sulfonylgroup, a phosphoryl group and an alkyl-substituted silyl group, or adivalent group composed of a combination of two or more of thesegroups); and residues of glycerol, xylitol, sorbitol, inositol,trimethylolpropane, ditrimethylpropane, neopentyl glycol orpolyglycerin.

In the foregoing formula (Z), preferred examples of A are a grouprepresented by any of following formulae (AI) to (AIII).

In the formulae, * means a bonding site to -D¹-(E)_(q)-D²-(B)_(m)—Z¹—R;C represents a carbon atom; R⁰ represents a hydrogen atom or asubstituent; each of X¹ to X⁴, X¹¹ to X¹⁴ and X²¹ to X²⁴ represents ahydrogen atom or a halogen atom (for example, a fluorine atom or achlorine atom) and may be the same as or different from every other;each of n1 to n3 represents an integer of from 0 to 5 and preferablyrepresents an integer of 1 or 2; and m4 represents an integer of from 0to 8 and preferably represents an integer of 0 or 2.

In the foregoing formula (AI), examples of the substituent representedby R⁰ include a substituted or non-substituted alkyl group having from 1to 50 carbon atoms (for example, in addition to methyl and ethyl, linearor branched propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosylor tetracosyl); an alkenyl group having from 2 to 35 carbon atoms (forexample, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, undecenyl or dodecenyl); a cycloalkyl group havingfrom 3 to 10 carbon atoms (for example, cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl or cycloheptyl); an aromatic ring group havingfrom 6 to 30 carbon atoms (for example, phenyl, naphthyl, biphenyl,phenanthryl or anthracenyl); a heterocyclic group (preferably a residueof a heterocyclic ring containing at least one hetero atom selectedamong a nitrogen atom, an oxygen atom and a sulfur atom; for example,pyridyl, pyrimidyl, triazinyl, thienyl, furyl, pyrrolyl, pyrazolyl,imidazolyl, triazolyl, thiazolyl, imidazolyl, oxazolyl, thiadialyl,oxadiazolyl, quinolyl or isoquinolyl); and a group composed of acombination of these groups. If possible, such a substituent may furtherhave one or more substituents, and examples of the substituent includean alkoxy group, an alkoxycarbonyl group, a halogen atom, an ethergroup, an alkyl carbonyl group, a cyano group, a thioether group, asulfoxide group, a sulfonyl group, an amide group, etc.

Though all of the compounds having a group represented by any of theformulae (AI) to (AIII) as A are preferable, from the viewpoint ofsynthesis, compounds having a group presented by the formula (AII),namely pentaerythritol derivatives are preferable.

In the formula (Z), L represents a single bond, an oxy group, asubstituted or non-substituted oxymethylene group represented byfollowing formula (A-a), or a substituted or non-substitutedoxyethyleneoxy group represented by following formula (A-b). Infollowing formulae, Alk represents a hydrogen atom, a C₁-C₆ alkyl groupor a cycloalkyl group.

—(O—C(Alk)₂)-  (A-a)

—(O—C(Alk)₂C(Alk)₂O)—  (A-b)

In the formula (Z), D¹ represents a carbonyl group (—C(═O)—) or asulfonyl group (—S(═O)₂—), and each D¹ may be the same as or differentfrom every other D¹; and D² represents a carbonyl group (—C(═O)—), asulfonyl group (—S(═O)₂—), a carboxyl group (—C(═O)O—), a sulfonyloxylgroup (—S(═O)₂O—), a carbamoyl group (—C(═O)N(Alk)-) or a sulfamoylgroup (—S(═O)₂N(Alk)-). Alk represents a hydrogen atom, a C₁-C₆ alkylgroup or a cycloalkyl group.

In the formula (Z), each E represents a single bond, a substituted ornon-substituted alkylene group (preferably a C₁-C₈ alkylene group; forexample, methylene, ethylene, propylene, butylene, pentylene, hexylene,heptylene or octylene), cycloalkylene group (preferably a C₃-C₁₅cycloalkylene group; for example, cyclopropylene, cyclobutylene,cyclopentylene or cyclohexylene), alkenylene group (preferably a C₂-C₈alkenylene group; for example, ethene, propene, butene or pentene),alkynylene group (preferably a C₂-C₈ alkynylene group; for example,ethyne, propyne, butyne or pentyne) or arylene group (preferably aC₆-C₁₀ arylene group; for example, phenylene), a divalent heterocyclicaromatic ring group or heterocyclic non-aromatic ring group, a divalentgroup selected among a substituted or non-substituted imino group, anoxy group, a sulfide group, a sulfenyl group, a sulfonyl group, aphosphoryl group and an alkyl-substituted silyl group, or a divalentgroup composed of a combination of two or more of these groups.

q represents an integer of 0 or more, and may be different from eachother when q is 2 or more.

In the foregoing formula (Z), preferred examples of -D¹-(E)_(q)-D²-include the following group.

In the foregoing formula, * represents a site bonding to L in theformula; and ** represents a site bonding to B in the formula. Each ofD¹¹ and D¹² represents a carbon atom or S(═O), and preferably a carbonatom. E¹ represents a single bond; a linear or branched, substituted ornon-substituted C₁-C₈ alkylene group, C₂-C₈ alkenylene group or C₂-C₈alkynylene group (provided that the carbon atom may be substituted withan oxygen atom); a substituted or non-substituted C₃-C₁₅ cycloalkylenegroup, cycloalkenylene group or cycloalkynylene group; a substituted ornon-substituted C₆-C₁₀ arylene group; a substituted or non-substitutedaromatic or non-aromatic heterocyclic group; —NH—; or —NH-Alk″-NH—(wherein Alk″ represents a C₁-C₄ alkylene group). Examples of thesubstituent of the alkylene group and the like include a halogen atom(for example, a fluorine atom or a chlorine atom). Preferred examples ofE¹ include a single bond and a divalent group such as methylene,ethylene, propylene, methyleneoxymethylene, vinylene, imino,tetrafluoroethylene, iminohexyleneimino, etc.

In the formula (Z), R represents a hydrogen atom, a substituted ornon-substituted C₈ or longer alkyl group, a perfluoroalkyl group or atrialkylsilyl group.

The C₈ or longer alkyl group represented by each R is preferably a C₁₂or longer alkyl group. Moreover, the alkyl group is preferably a C₃₀ orshorter alkyl group, and more preferably a C₂₀ or shorter alkyl group.The alkyl group may be either linear or branched. Specific examplesthereof include decyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl,tricosyl, octacosyl, triacontyl, pentatriacontyl, tetracontyl,pentacontyl, hexacontyl, octacontyl and decacontyl. Such an alkyl groupmay have one or more substituents. Examples of the substituent include ahalogen atom (for example, a fluorine atom and a chlorine atom), ahydroxyl group, an amino group, an alkylamino group, a mercapto group,an alkylthio group, an alkoxy group, a cyano group, etc.

The perfluoroalkyl group represented by each R is preferably a C₁-C₁₀perfluoroalkyl group, more preferably a C₁-C₆ perfluoroalkyl group,further preferably a C₁-C₄ perfluoroalkyl group, and especiallypreferably a C₁-C₂ perfluoroalkyl group. Examples thereof include atrifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group,a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group,a perfluoroheptyl group and a perfluorooctyl group.

The alkyl group bonding to Si of the trialkylsilyl group represented byeach R is preferably a C₁-C₄ alkyl group such as methyl, ethyl, etc.Such an alkyl group may be branched.

In the formula (Z), B varies depending upon R; in the case where Rrepresents a hydrogen atom or a substituted or non-substituted C₈ orlonger alkyl group, B represents a substituted or non-substitutedoxyethylene group or a substituted or non-substituted oxypropylenegroup; plural Bs connecting to each other may be the same as ordifferent from each other; and m represents a natural number of 1 ormore, preferably a number of from 4 to 20, and more preferably from 7 to12.

Each B may be the same as or different from every other B, and forexample, a plural kind of units B having a different chain length of thealkylene moiety from each other may be contained, and/or both a unit Bin which the alkylene moiety is non-substituted and a unit B in whichthe alkylene moiety is substituted may be contained. The alkylene moietyof the alkyleneoxy group may have a substituent, and examples of thesubstituent include a halogen atom (for example, a fluorine atom or achlorine atom). Moreover, the chain length of the substituted ornon-substituted oxyethylene group or the substituted or non-substitutedoxypropylene group may have distribution.

In the case where R represents a perfluoroalkyl group, B represents anoxyperfluoromethylene group, an oxyperfluoroethylene group or anoptionally branched oxyperfluoropropylene group (examples of thebranched oxyperfluoropropylene group include a perfluoroisopropylenegroup); plural Bs connecting to each other may be the same as ordifferent from each other; and m represents a natural number of 1 ormore, preferably a number of from 4 to 20, and more preferably from 7 to12.

In the case where R represents a trialkylsilyl group, B represents adialkylsiloxy group in which the alkyl group is selected among a methylgroup, an ethyl group and an optionally branched propyl group (examplesof the branched propyl group include an isopropyl group); each B may bethe same as or different from every other B; plural Bs connecting toeach other may be the same as or different from each other; and mrepresents a natural number of 1 or more, preferably a number of from 4to 20, and more preferably from 7 to 12.

In the formula (Z), Z¹ represents a single bond, a divalent groupselected among a carbonyl group, a sulfonyl group, a phosphoryl group,an oxy group, a substituted or non-substituted amino group, a sulfidegroup, an alkenylene group, an alkynylene group and an arylene group ora divalent group composed of a combination of two or more of thesegroups. As an example of the divalent connecting group, a divalentconnecting group composed of a combination of one or more membersselected among a carbonyl group, a sulfonyl group, a phosphoryl group,an oxy group, a substituted or non-substituted imino group, a sulfidegroup, a C₁-C₆ alkylene group, a C₁-C₁₆ cycloalkylene group, a C₂-C₈alkenylene group, a C₂-C₅ alkynylene group, a C₆-C₁₀ arylene group and aC₃-C₁₀ heterocyclic group is preferable. Examples of the connectinggroup composed of a combination of plural groups include —CONH—,—CO-cyclohexylene-, —CO—Rh— (wherein Rh represents a phenylene group;hereinafter the same), —CO—C≡C-Ph-, —CO—CH═CH-Ph-, —CO-Ph-N═N-Ph-O—,—C_(n)H_(2n)—NR— (n represents from 1 to 4; R represents a hydrogen atomor a C₁-C₄ alkyl group; and the right side is bonded to the end side)and —N,N′-pyrazylene-.

As described previously, in the formula (Z), each R may be the same asor different from every other R and represents a substituted ornon-substituted C₈ or longer alkyl group, a perfluoroalkyl group or atrialkylsilyl group. In more detail, as for —(B)_(m)—Z¹—R in the formula(Z), when R represents a substituted or non-substituted alkyl grouphaving 8 or more carbon atoms, following formula (ECa) is preferable;when R represents a perfluoroalkyl group, following formula (ECb) ispreferable; and when R represents a trialkylsilyl group, followingformula (ECa) is preferable.

In the formula (Z), when R represents a substituted or non-substitutedC₈ or longer alkyl group, —(B)_(m)—Z¹—R is preferably a grouprepresented by following formula (ECa).

In the formula (ECa), C represents a carbon atom; 0 represents an oxygenatom; L^(a) (corresponding to Z¹ in the formula (Z)) represents a singlebond or a divalent connecting group; each of X^(a1) and X^(a2)represents a hydrogen atom, a halogen atom or a substituent (preferablya hydrogen atom or a fluorine atom, and more preferably a hydrogenatom); na1 represents an integer of from 1 to 4; when na1 is 2 or more,plural X^(a1)s and X^(a2)s may be the same as or different from eachother; na2 represents a number of from 1 to 35 (preferably from 4 to 20,and more preferably from 4 to 10); and R^(a) (corresponding to R in theformula (Z)) represents a substituted or non-substituted C₈ or longeralkyl group (preferably C₁₂ or longer and also preferably C₃₀ orshorter, and more preferably C₂₄ or shorter).

L^(a) is preferably a single bond or a divalent connecting groupcomposed of a combination of one or more members selected among acarbonyl group, a sulfonyl group, a phosphoryl group, an oxy group, asubstituted or non-substituted amino group, a thio group, an alkylenegroup, an alkenylene group, an alkynylene group and an arylene group.

In the formula (Z), when R represents a perfluoroalkyl group,—(B)_(m)—Z¹—R is preferably a group represented by following formula(ECb).

In the formula (ECb), the same symbols as those in the formula (ECa) aresynonymous, respectively; L^(a1) corresponding to Z¹ in the formula (Z)represents a single bond; na2 represents a number of from 0 to 2; ncrepresents a number of from 1 to 10; m represents a number of from 1 to12; and n represents a number of from 1 to 6.

nc is preferably from 3 to 8. m is preferably a number of from 1 to 8,and more preferably from 1 to 4. n is preferably from 1 to 3.

Moreover, a preferred example of the formula (ECb) is a grouprepresented by following formula (ECb′).

In the formula (ECb′), the same symbols as those in the formula (ECb)are synonymous, and preferred ranges thereof are also the same. nc1 is 1or 2, and preferably 1.

In the formula (Z), when R represents a trialkylsilyl group,—(B)_(m)—Z¹—R is preferably a group represented by following formula(ECc).

In the formula (ECc), the same symbols as those in the formula (ECa) aresynonymous, respectively; each Alk′ may be the same as or different fromevery other Alk′ and represents a C₁-C₈ alkyl group; L^(a1)(corresponding to Z¹ in the formula (Z)) represents a single bond; andnb represents a number of from 1 to 10. nb is preferably a number offrom 2 to 20, and more preferably from 3 to 10.

In the foregoing formula (Z), p represents an integer of 2 or more,preferably 3 or more, and more preferably from 3 to 8. In view of thefact that the compound of the formula (Z) has plural side chains havinga prescribed structure, it is able to achieve a low coefficient offriction.

Examples of the compound represented by the formula (Z) are given below,but it should not be construed that the invention is limited thereto.

(AI)

Com- pound No. R⁰ Y¹ = Y² = Y³ R¹ R² R³ AI-1 C₂H₅ COC₂H₄CO₂(C₂H₄O)_(6.5)C₂₂H₄₄-n (C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n AI-2C₂H₅ COC₂H₄CO₂ (C₂H₄O)_(6.5)C₂₀H₄₁-n (C₂H₄O)_(6.5)C₂₀H₄₁-n(C₂H₄O)_(6.5)C₂₀H₄₁-n AI-3 C₂H₅ COC₂H₄CO₂ (C₂H₄O)_(6.5)C₁₈H₃₇-n(C₂H₄O)_(6.5)C₁₈H₃₇-n (C₂H₄O)_(6.5)C₁₈H₃₇-n AI-4 C₂H₅ COC₂H₄CO₂(C₂H₄O)_(6.5)C₁₆H₃₃-n (C₂H₄O)_(6.5)C₁₆H₃₃-n (C₂H₄O)_(6.5)C₁₆H₃₃-n AI-5C₂H₅ COC₂H₄CO₂ (C₂H₄O)_(6.5)C₁₄H₂₉-n (C₂H₄O)_(6.5)C₁₄H₂₉-n(C₂H₄O)_(6.5)C₁₄H₂₉-n AI-6 C₂H₅ COC₂H₄CO₂ (C₂H₄O)_(6.5)C₁₂H₂₅-n(C₂H₄O)_(6.5)C₁₂H₂₅-n (C₂H₄O)_(6.5)C₁₂H₂₅-n AI-7 C₂H₅ COC₂H₄CO₂(C₂H₄O)_(6.5)C₂₆H₅₃-n (C₂H₄O)_(6.5)C₂₆H₅₃-n (C₂H₄O)_(6.5)C₂₆H₅₃-n AI-8C₂H₅ COC₂H₄CO₂ (C₂H₄O)_(6.5)C₃₅H₇₁-n (C₂H₄O)_(6.5)C₃₅H₇₁-n(C₂H₄O)_(6.5)C₃₅H₇₁-n AI-9 CH₃ COC₂H₄CO₂ (C₂H₄O)_(6.5)CH(C₆H₁₃-n)C₉H₁₉-n(C₂H₄O)_(6.5)- (C₂H₄O)_(6.5)CH- CH(C₆H₁₃-n)C₉H₁₉-n (C₆H₁₃-n)C₉H₁₉-nAI-10 CH₃ COC₂H₄CO₂ (C₂H₄O)_(6.5)CH(C₆H₁₃-n)C₉H₁₉-n(C₂H₄O)_(6.5)C₁₈H₃₇-n (C₂H₄O)_(6.5)C₂₀H₄₁-n AI-11 CH₃ COC₂H₄CO₂(C₂H₄O)₄COC₂₁H₄₃-n (C₂H₄O)₄COC₂₁H₄₃-n (C₂H₄O)₄COC₂₁H₄₃-n AI-12 CH₃COC₂H₄CO₂ (C₂H₄O)_(6.2)CONHC₁₈H₃₇-n (C₂H₄O)_(6.2)- (C₂H₄O)_(6.2)-CONHC₁₈H₃₇-n CONHC₁₈H₃₇-n AI-13 CH₃ COC₂H₄CO₂(C₂H₄O)_(6.2)COC₆H₄C₁₈H₃₇-n (C₂H₄O)_(6.2)- (C₂H₄O)_(6.2)- COC₆H₄C₁₈H₃₇-nCOC₆H₄C₁₈H₃₇-n AI-14 CH₃ COC₂H₄CO₂ (C₂H₄O)₄PO₂C₂₁H₄₃-n(C₂H₄O)₄PO₂C₂₁H₄₃-n (C₂H₄O)₄PO₂C₂₁H₄₃-n AI-15 CH₃ COC₂H₄CO₂(C₂H₄O)₄SO₂C₁₈H₃₇-n (C₂H₄O)₄SO₂C₁₈H₃₇-n (C₂H₄O)₄SO₂C₁₈H₃₇-n AI-16 CH₃COC₂H₄CO₂ (C₂H₄O)_(6.2)COC≡CC₆H₄C₁₈H₃₇-n (C₂H₄O)_(6.2)- (C₂H₄O)_(6.2)-COC≡CC₆H₄C₁₈H₃₇-n COC≡CC₆H₄C₁₈H₃₇-n AI-17 CH₃ COC₂H₄CO₂(C₂H₄O)_(6.2)COCH≡CHC₆H₄C₁₈H₃₇-n (C₂H₄O)_(6.2)- (C₂H₄O)_(6.2)-COCH≡CHC₆H₄C₁₈H₃₇-n COCH≡CHC₆H₄C₁₈H₃₇-n AI-18 CH₃ COC₂H₄CO₂(C₂H₄O)_(6.2)C₂H₄N(CH₃)C₁₈H₃₇-n (C₂H₄O)_(6.2)- (C₂H₄O)_(6.2)-C₂H₄N(CH₃)C₁₈H₃₇-n C₂H₄N(CH₃)C₁₈H₃₇-n AI-19 CH₃ COC₂H₄CO₂(C₃H₆O)₃C₁₆H₃₃-n (C₃H₆O)₃C₁₆H₃₃-n (C₃H₆O)₃C₁₆H₃₃-n AI-20 CH₃ COC₂H₄CO₂(C₃H₆O)₃₂(C₂H₄O)₄COC₂₁H₄₃-n (C₃H₆O)₃₂- (C₃H₆O)₃₂- (C₂H₄O)₄COC₂₁H₄₃-n(C₂H₄O)₄COC₂₁H₄₃-n AI-21 CH₃ COC₂H₄CO₂ (C₃H₆O)₃₂(C₂H₄O)₄COC₂₂H₄₅-n(C₃H₆O)₃₂- (C₃H₆O)₃₂- (C₂H₄O)₄COC₂₂H₄₅-n (C₂H₄O)₄COC₂₂H₄₅-n AI-22 CH₃COCH₂CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n(C₂H₄O)_(6.5)C₂₂H₄₅-n AI-23 CH₃ COC₃H₆CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n(C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n AI-24 CH₃ COC₄H₈CO₂(C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n AI-25CH₃ COCH═CHCO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n(C₂H₄O)_(6.5)C₂₂H₄₅-n AI-26 CH₃ COCH₂OCH₂CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n(C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n AI-27 CH₃ 1.2-COC₆H₄CO₂(C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n AI-28C₆H₅ 1.4-COC₆H₄CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n(C₂H₄O)_(6.5)C₂₂H₄₅-n AI-29 C₆H₅ COCH₂C(CH3)₂CH₂CO₂(C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n AI-30C₂F₅ COC₂F₄CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n(C₂H₄O)_(6.5)C₂₂H₄₅-n AI-31 C₂F₅ 1.2-COC₆F₄CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n(C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n AI-32 C₂F₅ CONHCO₂(C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n AI-33C₂F₅ CONHSO₃ (C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n(C₂H₄O)_(6.5)C₂₂H₄₅-n AI-34 C₂F₅ SO2NHCO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n(C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n AI-36 C₂F₅ COCO₂(C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)₆₅C₂₂H₄₅-n AI-37 C₂F₅COC₂H₄CO₂ (C₂H₄O)_(10.3)C₂₂H₄₅-n (C₂H₄O)_(10.3)C₂₂H₄₅-n(C₂H₄O)_(10.3)C₂₂H₄₅-n AI-38 C₂F₅ COC₂H₄CO₂ (C₂H₄O)_(19.7)C₂₂H₄₅-n(C₂H₄O)_(19.7)C₂₂H₄₅-n (C₂H₄O)_(19.7)C₂₂H₄₅-n AI-39 C₅H₄N COC₂H₄CO₂(C₂H₄O)_(35.2)C₂₂H₄₅-n (C₂H₄O)_(35.2)C₂₂H₄₅-n (C₂H₄O)_(35.2)C₂₂H₄₅-n(AI)

Com- pound No. R⁰ n1 n2 n3 Y¹ = Y² = Y³ R¹ R² R³ AI-42 C₅H₄N 4 4 4COC₂H₄CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n(C₂H₄O)_(6.5)C₂₂H₄₅-n AI-43 H 1 1 1 COC₂H₄CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n(C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n AI-44 H 1 1 1 COC₂H₄CO₂(C₂H₄O)_(6.5)CH(C₆H₁₃-n)C₉H₁₉-n (C₂H₄O)_(6.5)- (C₂H₄O)_(6.5)-CH(C₆H₁₃-n)C₉H₁₉-n CH(C₆H₁₃-n)C₉H₁₉-n AI-45 H 1 1 1 COC₂H₄CO₂(C₂H₄O)_(6.2)CONHC₁₅H₃₁-n (C₂H₄O)_(6.2)- (C₂H₄O)_(6.2)- CONHC₁₅H₃₁-nCONHC₁₅H₃₁-n AI-55 H 1 1 1 CONHC₆H₁₂NHCO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n(C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n AI-56 C₂H₅ 1 1 1CONHC₆H₁₂NHCO₂ (C₂H₄O)_(6.5)C₁₅H₃₁-n (C₂H₄O)_(6.5)C₁₅H₃₁-n(C₂H₄O)_(6.5)C₁₅H₃₁-n AI-57 C₂H₅ 1 1 1 CONHC₆H₁₂NHCO₂(C₂H₄O)_(6.5)C₂₆H₅₃-n (C₂H₄O)_(6.5)C₂₆H₅₃-n (C₂H₄O)_(6.5)C₂₆H₅₃-n AI-58C₂H₅ 1 1 1 CONHC₆H₁₂NHCO₂ (C₂H₄O)_(6.5)CH(C₆H₁₃-n)C₉H₁₉-n (C₂H₄O)_(6.5)-(C₂H₄O)_(6.5)- CH(C₆H₁₃-n)C₉H₁₉-n CH(C₆H₁₃-n)C₉H₁₉-n AI-59 C₂H₅ 1 1 1CONHC₆H₁₂NHCO₂ (C₂H₄O)₄COC₂₁H₄₃-n (C₂H₄O)₄COC₂₁H₄₃-n (C₂H₄O)₄COC₂₁H₄₃-nAI-60 C₂H₅ 1 1 1 CONHC₆H₁₂NHCO₂ (C₂H₄O)₄COC₂₁H₄₃-n (C₂H₄O)₄COC₂₁H₄₃-n(C₂H₄O)₄COC₂₁H₄₃-n AI-61 C₂H₅ 1 1 0 CONHC₆H₁₂NHCO₂ (C₂H₄O)₄COC₂₁H₄₃-n(C₂H₄O)₄COC₂₁H₄₃-n (C₂H₄O)₄COC₂₁H₄₃-n AI-62 C₂H₅ 1 0 0 CONHC₆H₁₂NHCO₂(C₂H₄O)₄COC₂₁H₄₃-n (C₂H₄O)₄COC₂₁H₄₃-n (C₂H₄O)₄COC₂₁H₄₃-n AI-63 C₂H₅ 0 00 CONHC₆H₁₂NHCO₂ (C₂H₄O)₄COC₂₁H₄₃-n (C₂H₄O)₄COC₂₁H₄₃-n(C₂H₄O)₄COC₂₁H₄₃-n AI-64 C₂H₅ 1 1 0 COCH₂CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n(C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n AI-65 C₂H₅ 1 0 0 COCH₂CO₂(C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n AI-66C₂H₅ 1 0 0 COCH₂CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n (C₂H₄O)_(6.5)C₂₂H₄₅-n(C₂H₄O)_(6.5)C₂₂H₄₅-n (AI)

Compound No. Y¹ Y² Y³ R¹ = R² = R³ AI-67 COCH₂CO₂ COC₂H₄CO₂ COC₂H₄CO₂(C₂H₄O)_(10.3)C₈H₁₇-n AI-68 COCH₂CO₂ COC₂H₄CO₂ COC₂H₄CO₂(C₂H₄O)_(19.7)C₈H₁₇-n AI-69 COCH₂CO₂ COC₂H₄CO₂ COC₂H₄CO₂(C₂H₄O)_(15.2)C₈H₁₇-n AI-70 COCH₂CO₂ COCH₂CO₂ COCH₂CO₂(C₂H₄O)_(15.2)C₈H₁₇-n AI-71 CONHCO₂ COC₂H₄CO₂ COC₂H₄CO₂(C₂H₄O)_(15.2)CH₂CF₂O(C₂F₄O)₂C₂F₅-n AI-72 CONHSO₃ COC₂H₄CO₂ COC₂H₄CO₂(C₂H₄O)_(15.2)CH₂CF₂O(C₂F₄O)₂C₂F₅-n AI-73 SO2NHCO₂ COC₂H₄CO₂ COC₂H₄CO₂(C₂H₄O)_(15.2)CH₂CF₂O(C₂F₄O)₂C₂F₅-n AI-74 CSNHCO₂ COC₂H₄CO₂ COC₂H₄CO₂(C₂H₄O)_(15.2)CH₂CF₂O(C₂F₄O)₂C₂F₅-n AI-75 COCO₂ COC₂H₄CO₂ COC₂H₄CO₂(C₂H₄O)_(15.2)CH₂CF₂O(C₂F₄O)₂C₂F₅-n AI-76 COC₂H₄CO₂ COC₂H₄CO₂ COC₂H₄CO₂(C₂H₄O)_(10.3)(SiMe₂O)₄SiMe₃-n AI-77 COCH₂CO₂ COC₂H₄CO₂ COC₂H₄CO₂(C₂H₄O)_(10.3)(SiMe₂O)₄SiMe₃-n AI-78 CONHCO₂ COC₂H₄CO₂ COC₂H₄CO₂(C₂H₄O)_(10.3)(SiMe₂O)₄SiMe₃-n AI-79 CONHSO₃ COC₂H₄CO₂ COC₂H₄CO₂(C₂H₄O)_(10.3)(SiMe₂O)₄SiMe₃-n

(AII)

Compound No. Y¹ = Y² = Y³ = Y⁴ R¹ = R² = R³ = R⁴ AII-1 COC₂H₄CO₂(C₂H₄O)_(6.5)C₂₂H₄₅-n AII-2 COC₂H₄CO₂ (C₂H₄O)_(4.0)C₂₂H₄₅-n AII-3COC₂H₄CO₂ (C₂H₄O)_(6.52)C₂₀H₄₁-n AII-4 COC₂H₄CO₂ (C₂H₄O)_(6.55)C₁₈H₃₇-nAII-5 COC₂H₄CO₂ (C₂H₄O)₄C₁₈H₃₇-n AII-6 COC₂H₄CO₂ (C₂H₄O)_(6.42)C₁₆H₃₃-nAII-7 COC₂H₄CO₂ (C₂H₄O)_(6.15)C₁₄H₂₉-n AII-8 COC₂H₄CO₂ (C₂H₄O)₄C₁₄H₂₉-nAII-9 COC₂H₄CO₂ (C₂H₄O)_(6.5)C₁₂H₂₅-n AII-10 COC₂H₄CO₂(C₂H₄O)_(6.5)C₂₆H₅₃-n AII-11 COC₂H₄CO₂ (C₂H₄O)_(6.5)C₃₅H₇₁-n AII-12COC₂H₄CO₂ (C₂H₄O)_(3.0)C₂₂H₄₅-n AII-13 COC₂H₄CO₂ (C₂H₄O)_(4.0)C₂₂H₄₆-nAII-14 COC₂H₄CO₂ (C₂H₄O)_(6.18)C₂₂H₄₅-n AII-15 COC₂H₄CO₂(C₂H₄O)_(7.8)C₂₂H₄₆-n AII-16 COC₂H₄CO₂ (C₂H₄O)_(8.4)C₂₂H₄₇-n AII-17COC₂H₄CO₂ (C₂H₄O)_(10.3)C₂₂H₄8-n AII-18 COC₂H₄CO₂ (C₂H₄O)_(19.0)C₂₂H₄₉-nAII-19 COC₂H₄CO2 (C₂H₄O)_(27.7)C₂₂H₅₀-n AII-20 COC₂H₄CO2(C₂H₄O)_(6.5)CH₂CH(C₆H₁₃-n)C₉H₁₉-n Com- pound No. Y¹ = Y² =Y³ =Y⁴ R¹ R²R³ R⁴ AII-21 COC₂H₄CO₂ (C₂H₄O)_(6.5)CH₂CH(C₆H₁₃-n)C₉H₁₉-n(C₂H₄O)_(6.5)C₁₈H₃₇-n (C₂H₄O)_(6.5)C₂₀H₄₁-n (C₂H₄O)_(6.5)C₂0H₄₁-nCompound No. Y¹ = Y²= Y³= Y⁴ R¹ = R² = R³ = R⁴ AII-22 COC₂H₄CO₂(C₂H₄O)₄COC₂₁H₄₃-n AII-23 COC₂H₄CO₂ (C₂H₄O)_(6.2)CONHC₁₈H₃₇-n AII-24COC₂H₄CO₂ (C₂H₄O)_(6.2)COC₆H₄C₁₈H₃₇-n AII-25 COC₂H₄CO₂(C₂H₄O)₄PO₂C₂₁H₄₃-n AII-26 COC₂H₄CO₂ (C₂H₄O)₄SO₂C₁₈H₃₇-n AII-27COC₂H₄CO₂ (C₂H₄O)_(6.2)COC≡CC₆H₄C₁₈H₃₇-n AII-28 COC₂H₄CO₂(C₂H₄O)_(6.2)COCH═CHC₆H₄C₁₈H₃₇-n AII-29 COC₂H₄CO₂(C₂H₄O)_(6.2)C₂H₄N(CH₃)C₁₈H₃₇-n AII-30 COC₂H₄CO₂ (C₃H₆O)₅C₁₆H₃₃-n AII-31COC₂H₄CO₂ (C₃H₆O)_(5.2)(C₂H₄O)₄COC₂₁H₄₃-n AII-32 COC₂H₄CO₂(C₃H₆O)_(5.2)(C₂H₄O)₄C₂₂H₄₅-n AII-33 COCH₂CO₂ (C₂H₄O)_(6.18)C₂₂H₄₅-nAII-34 COC₃H₆CO₂ (C₂H₄O)_(6.18)C₂₂H₄₅-n AII-35 COC₄H₈CO₂(C₂H₄O)_(6.18)C₂₂H₄₅-n AII-36 COCH═CHCO₂ (C₂H₄O)_(6.18)C₂₂H₄₅-n AII-37COCH₂OCH₂CO₂ (C₂H₄O)_(6.18)C₂₂H₄₅-n AII-38 1.2-COC₆H₄CO₂(C₂H₄O)_(6.18)C₂₂H₄₅-n AII-39 1.4-COC₆H₄CO₂ (C₂H₄O)_(6.18)C₂₂H₄₅-nAII-40 COCH₂C(CH3)₂CH₂CO₂ (C₂H₄O)_(6.18)C₂₂H₄₅-n AII-41 COC₂F₄CO₂(C₂H₄O)_(6.18)C₂₂H₄₅-n AII-43 1.2-COC₆F₄CO₂ (C₂H₄O)_(6.18)C₂₂H₄₅-nAII-44 COCH₂OCH₂CO₂ (C₂H₄O)_(6.18)C₂₂H₄₅-n AII-46 COCH₂OCH₂CO₂(C₂H₄O)₄COC₂₁H₄₃-n AII-47 COC₂H₄CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n AII-48COC₂H₄CO₂ (C₂H₄O)_(4.9)C₂₂H₄₅-n AII-49 COC₂H₄CO₂(C₂H₄O)_(6.39)CH₂CH(C₇H₁₅-n)C₉H₁₉-n AII-50 COC₂H₄CO₂(C₂H₄O)_(6.2)CONHC₁₈H₃₇-n AII-51 COC(CH₃)₂CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-nAII-52 COC(CH₃)₂CO₂ (C₂H₄O)_(6.5)CH(C₆H₁₃-n)C₉H₁₉-n AII-53 COC(CH₃)₂CO₂(C₂H₄O)₄COC₂₁H₄₃-n AII-54 COCH═CHCO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n AII-55COCH═CHCO₂ (C₂H₄O)_(6.5)C₁₈H₃₇-n AII-56 COCH═CHCO₂ (C₂H₄O)₄COC₂₁H₄₃-nAII-57 COCH═CHCO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n AII-59 COCH₂NCH₃CO₂(C₂H₄O)_(6.5)C₂₂H₄₅-n AII-60 CONHC₆H₁₂NHCO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n AII-61CONHC₆H₁₂NHCO₂ (C₂H₄O)_(6.55)C₁₈H₃₇-n AII-62 CONHC₆H₁₂NHCO₂(C₂H₄O)_(6.5)C₂₆H₅₃-n AII-63 CONHC₆H₁₂NHCO₂(C₂H₄O)_(6.5)CH₂CH(C₆H₁₃-n)C₉H₁₉-n AII-64 CONHC₆H₁₂NHCO₂(C₂H₄O)₄COC₂₁H₄₃-n AII-65 COC₂H₄CO₂ A: (C₂H₄O)_(6.5)C₂₂H₄₅-n B:(C₂H₄O)_(6.39)CH₂CH{C₂H₄CH(CH₃)C₃H₇-n}C₄H₈CH(CH₃)C₃H₇-n A:B = 0:100AII-66 COC₂H₄CO₂ A: (C₂H₄O)_(6.5)C₂₂H₄₅-n B:(C₂H₄O)_(6.39)CH₂CH{C₂H₄CH(CH₃)C₃H₇-n}C₄H₈CH(CH₃)C₃H₇-n A:B = 99:1AII-67 COC₂H₄CO₂ A: (C₂H₄O)_(6.5)C₂₂H₄₅-n B:(C₂H₄O)_(6.39)CH₂CH{C₂H₄CH(CH₃)C₃H₇-n}C₄H₈CH(CH₃)C₃H₇-n A:B = 95:5AII-68 COC₂H₄CO₂ A: (C₂H₄O)_(6.5)C₂₂H₄₅-n B:(C₂H₄O)_(6.39)CH₂CH{C₂H₄CH(CH₃)C₃H₇-n}C₄H₈CH(CH₃)C₃H₇-n A:B = 90:10AII-69 COC₂H₄CO₂ A: (C₂H₄O)_(6.5)C₂₂H₄₅-n B:(C₂H₄O)_(6.39)CH₂CH{C₂H₄CH(CH₃)C₃H₇-n}C₄H₈CH(CH₃)C₃H₇-n A:B = 80:20AII-70 CONHCO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n AII-71 CONHSO₃(C₂H₄O)_(6.5)C₂₂H₄₅-n AII-72 SO2NHCO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n AII-74 COCO₂(C₂H₄O)_(6.5)C₂₂H₄₅-n AII-75 COC₂H₄CO₂ (C₂H₄O)_(10.3)C₈H₁₇-n AII-76COC₂H₄CO₂ (C₂H₄O)_(19.7)C₈H₁₇-n AII-77 COC₂H₄CO₂ (C₂H₄O)_(15.2)C₈H₁₇-nAII-78 COCH₂CO₂ (C₂H₄O)_(15.2)C₈H₁₇-n AII-79 CONHCO₂(C₂H₄O)_(15.2)CH₂CF₂O(C₂F₄O)₂C₂F₅-n AII-80 CONHSO₃(C₂H₄O)_(15.2)CH₂CF₂O(C₂F₄O)₂C₂F₅-n AII-81 SO2NHCO₂(C₂H₄O)_(15.2)CH₂CF₂O(C₂F₄O)₂C₂F₅-n AII-83 COCO₂(C₂H₄O)_(15.2)CH₂CF₂O(C₂F₄O)₂C₂F₅-n AII-84 COC₂H₄CO₂(C₂H₄O)_(10.3)(SiMe₂O)₄SiMe₃-n AII-85 COCH₂CO₂(C₂H₄O)_(10.3)(SiMe₂O)₄SiMe₃-n AII-86 CONHCO₂(C₂H₄O)_(10.3)(SiMe₂O)₄SiMe₃-n AII-87 CONHSO₃(C₂H₄O)_(10.3)(SiMe₂O)₄SiMe₃-n AII-88 COC₂H₄CO₂ (C₂H₄O)_(10.0)C₁₈H₃₇-nAII-89 COC₂H₄CO₂ (C₂H₄O)_(10.0)C₁₂H₂₅-n AII-90 COC₂H₄CO₂(C₂H₄O)_(10.0)C₂₂H₄₅-n

(AIII)

Compound No. M Y R AIII-1 0 COC₂H₄CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n AIII-2 1COC₂H₄CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n AIII-3 2 COC₂H₄CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-nAIII-4 3 COC₂H₄CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n AIII-5 0 COC₂H₄CO₂(C₂H₄O)₄COC₂₁H₄₃-n AIII-6 0 COC₂H₄CO₂ A: (C₂H₄O)_(6.5)C₂₂H₄₅-n B:(C₂H₄O)_(6.5)CH{C₂H₄CH(CH₃)C₃H₇-n}C₄H₈CH(CH₃)C₃H₇-n A:B = 95:5 AIII-7 2COCH₂OCH₂CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n AIII-8 0 CONHC₆H₁₂NHCO₂(C₂H₄O)_(6.5)C₂₂H₄₅-n AIII-9 3 CONHC₆H₁₂NHCO₂ (C₂H₄O)_(6.5)C₂₀H₄₁-nAIII-10 1 CONHC₆H₁₂NHCO₂ (C₂H₄O)_(6.5)C₁₈H₃₇-n AIII-11 1 CONHC₆H₁₂NHCO₂(C₂H₄O)₄C₁₈H₃₇-n AIII-12 2 CONHC₆H₁₂NHCO₂ (C₂H₄O)_(6.5)C₁₆H₃₃-n AIII-132 CONHC₆H₁₂NHCO₂ (C₂H₄O)_(6.5)C₁₄H₂₉-n AIII-14 3 CONHC₆H₁₂NHCO₂(C₂H₄O)₄C₁₄H₂₉-n AIII-15 3 CONHC₆H₁₂NHCO₂ (C₂H₄O)_(6.5)C₁₂H₂₅-n AIII-163 COCH₂CO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n AIII-17 3 CONHCO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-nAIII-18 3 CONHSO₃ (C₂H₄O)_(6.5)C₂₂H₄₅-n AIII-19 3 SO2NHCO₂(C₂H₄O)_(6.5)C₂₂H₄₅-n AIII-21 3 COCO₂ (C₂H₄O)_(6.5)C₂₂H₄₅-n AIII-22 3COC₂H₄CO₂ (C₂H₄O)_(10.3)C₂₂H₄₅-n AIII-23 3 COC₂H₄CO₂(C₂H₄O)_(19.7)C₂₂H₄₅-n AIII-24 3 COC₂H₄CO₂ (C₂H₄O)_(15.2)C₂₂H₄₅-nAIII-25 3 COC₂H₄CO₂ (C₂H₄O)_(10.3)C₈H₁₇-n AIII-26 3 COC₂H₄CO₂(C₂H₄O)_(19.7)C₈H₁₇-n AIII-27 3 COC₂H₄CO₂ (C₂H₄O)_(15.2)C₈H₁₇-n AIII-283 COCH₂CO₂ (C₂H₄O)_(15.2)C₈H₁₇-n AIII-29 3 CONHCO₂(C₂H₄O)_(15.2)CH₂CF₂O(C₂F₄O)₂C₂F₅-n AIII-30 3 CONHSO₃(C₂H₄O)_(15.2)CH₂CF₂O(C₂F₄O)₂C₂F₅-n AIII-31 3 SO2NHCO₂(C₂H₄O)_(15.2)CH₂CF₂O(C₂F₄O)₂C₂F₅-n AIII-33 3 COCO₂(C₂H₄O)_(15.2)CH₂CF₂O(C₂F₄O)₂C₂F₅-n AIII-34 3 COC₂H₄CO₂(C₂H₄O)_(10.3)(SiMe₂O)₄SiMe₃-n AIII-35 3 COCH₂CO₂(C₂H₄O)_(10.3)(SiMe₂O)₄SiMe₃-n AIII-36 3 CONHCO₂(C₂H₄O)_(10.3)(SiMe₂O)₄SiMe₃-n AIII-37 3 CONHSO₃(C₂H₄O)_(10.3)(SiMe₂O)₄SiMe₃-n

The compounds represented by the foregoing formulae (Z) can be producedby utilizing various organic synthesis reactions. For example, in theformula (Z), the compound in which A is a group represented by any ofthe formulae (AI) to (AIII) is basically formed through connectionbetween a polyhydric alcohol such as glycerol, pentaerythritol, etc. anda side chain structure, but in general, an esterification reaction isfrequently adopted. For example, the compound can be produced by acondensation reaction between a polyhydric alcohol and an acid chlorideof a side chain carboxylic acid, an isocyanate having a side chainstructure or an alkyl halide having a side chain structure, or acombination of various reactions of open-ring type esterification of apolyhydric alcohol and succinic anhydride or Meldrum's acid to form acarboxylic acid and esterification of an acid chloride thereof and analcohol having a side chain structure, or the like. Moreover, the sidechain structure portion can be easily produced by using a long-chainalkyl alcohol or an alcohol obtained by adding an ethylene oxide gas toa carboxylic acid, or further using succinic acid, Meldrum's acid or ahalocarboxylic acid.

3. Properties of Compound of the Invention

When the compound of the foregoing formula (Z) is dispersed in an oilymedium, it forms a coating film in the process in which it is graduallysegregated at a high load under a high pressure in a high shear fielddue to a characteristic feature on the common chemical structure andmade high in a concentration, and as compared with the conventional rawmaterials, it exhibits relatively low friction properties in an elasticfluid lubrication region because of a low viscosity-pressure modulus(low α). In addition, for the same reason (low α), it may be conjecturedthat such a compound has a wide pressure range for keeping avisco-elastic film and can be prevented from occurrence of the contactwith a sliding surface, and as a result, wear resistance is realized.

As for this phenomenon, the present inventor spectrally observed aneighborhood of a point-contacting portion of an instrument named apoint contact EHL evaluation apparatus for evaluating an elastic fluidlubrication region in the field of tribology and succeeded inquantitatively grasping a change of material concentration at a highload in a high shear field. Specifically, the observation was carriedout in the following manner. First of all, the foregoing compound isdispersed in an oily medium to prepare a sample. Separately, a rotatingsteel ball is placed on a diamond (hard plane) plate while making itsrotation axis parallel, and a load is applied to the axis, therebybringing them into press contact with each other. The prepared sample isfed and flown in a gap between the rotating steel ball and the diamondplate and its neighborhood.

Though a Newtonian ring which is an optical interference pattern isformed in a portion where the steel ball comes into point contact withthe diamond plate, by irradiating infrared rays from the opposite sideto the steel ball via the diamond plate and reflecting them on the steelball, an IR spectrum of a thin film of the sample in the vicinity of theNewtonian ring can be measured. This method is an analysis method of aminute portion in the tribology field described in Junichi ISHIKAWA,Hidetaka NANAO, Ichiro MINAMI and Shigeyuki MORI, Preprint of theInternational Tribology Conference (Tottori, 2004-11), page 243 and isnot special. However, according to this method, by changing a rotationspeed of the steel ball, a load to the rotation axis and a temperatureof the sample, the behavior under various elastic fluid lubricationconditions can be observed on the spot, and this method is an effectivemethod.

When a mineral oil or a poly-α-olefin is used as the oily medium whichis used for the preparation of a sample used for the measurement, sincesuch a compound is a hydrocarbon, it is free from characteristicabsorption other than C—C and C—H. In consequence, when the foregoingcompound has a functional group exhibiting a distinct high-intensitycharacteristic absorption band, such as a carbonyl group of an esterbond, a cyano group, an ethynyl group, a perfluoroalkyl group, asiloxane group, etc., a change in the concentration can bequantitatively detected from the intensity of the characteristicabsorption band.

As a result of observation using the foregoing apparatus, it was notedthat in a so-called Hertzian area under a high pressure in a high shearfield, where a Newtonian ring is formed, the foregoing compound isgradually segregated in a form of a candle flame formed by partition ofa flow of the sample in, for example, a region of from 20 to 400 μmbackward. In many cases, the concentration becomes substantiallyconstant for about 5 minutes to 2 hours under a condition at ameasurement temperature of 40° C. at a linear velocity of 0.15 m/secunder a Hertzian pressure of 0.3 GPa, an aspect of which is, however,different depending upon a condition such as a temperature, etc.

The foregoing point contact EHL evaluation apparatus is a model of theHertzian contact area under a high-pressure and high-shear condition,namely a true contact site, and the actual friction contact area is anarea where such true contact areas are crowded. Therefore, it may beconsidered that the composition of the invention containing theforegoing compound in the oily medium accumulates the foregoing compoundin the vicinity of a number of true contact areas of such a frictioncontact area.

In consequence, the foregoing high-viscosity compound is segregated in asliding part by the oily medium, and a smooth film is formed by a highshear force, whereby its gap becomes narrower than the usual. Therefore,such a low-viscosity oily medium is formed into a thinner film, therebycontributing to low friction of fluid lubrication, and in a fluidlubrication region, a driving machine thereof drives with highefficiency from the energy standpoint. And in a high-load andhigh-pressure field, it is probable that the foregoing compound isgradually accumulated before the low-viscosity oily medium is brokenfrom the elasto-plastic body film, and therefore, in the case where theviscosity-pressure modulus α of the foregoing compound having beendispersed in the low-viscosity oily medium is small, the viscositybecomes relatively low, and in the contact site, a low coefficient offriction is revealed by a low-viscosity elastic fluid lubricating filmmade of the subject compound. Under such a high-load condition, thecontact area is increased due to an elastic strain of the interface rawmaterial, and a pressure in that portion is lowered. Therefore, a muchmore mild condition is realized; and even under a condition under whichcurrent lubricating oils already come into a boundary lubricationregion, a favorable lubrication region where the both interfaces do notsubstantially come into contact with each other due to the low-viscosityelastic fluid lubricating film of the foregoing compound is kept. As aresult, fuel saving is achieved.

Recent fuel-saving type engine oils containing a molybdenum basedorganometallic complex exhibit low viscosity such that a viscosity at40° C. is not more than 30 mPa·s and are marketed as a multi-gradelow-viscosity oil such as 0W-20 or the like. However, as describedpreviously, in the composition of the invention, in view of the factthat an elastic fluid lubricating film is formed before thelow-viscosity based oil is broken, the foregoing compound is able toreveal the same effects of low friction and wear resistance under ahigh-pressure and high-shear condition at a high temperature. Moreover,substantial low viscosity is revealed by the elastic fluid film evenunder such a severe condition, and the low-viscosity base oilpreferentially functions under a mild condition; and therefore, anincrease of the viscosity at middle to low temperatures to be caused dueto a viscosity index improver as in current lubricants does not occur.

Moreover, since the composition of the invention does not basicallyutilize a reaction with the interface, the film forming propertiesthereof are not restricted by the material quality of the interface. Inaddition, since the foregoing compound is basically strong against heatand chemically stable, it is relatively conspicuously high indurability. Moreover, the friction portion disappears under a high-loadcondition, and when the temperature is high, the compound of theinvention is again dispersed in the oily medium, whereby the totalamount is always kept. When needed, a necessary amount of the compoundis accumulated to reveal low friction, and when not needed, the compoundis again dispersed; and thus, the composition of the invention is anextremely intelligent lubricant composition.

On the other hand, in the case where the foregoing compound exhibitshigh a, the composition effectively functions as a traction oil which isused in a site of, for example, transmitting a power by friction of aclutch, etc. In conventional high-function traction oils, hydrocarbonshaving an incorruptible structure, all of which have a highviscosity-pressure modulus, have been used; however, a defect thereofresides in a point that an atmospheric viscosity of the oil itself mustbecome relatively high. This matter decreases a driving efficiency in anormal state. However, a composition in which a raw material having ahigh viscosity-pressure modulus among the foregoing compounds isdispersed in a low-viscosity oily medium enables one to make both fuelconsumption efficiency and effective transmission of a power compatiblewith each other. The low-viscosity oily medium occupying the majority ofthe transmission oil is able to effectively reduce a friction loss dueto viscosity in a region other than a driving power transmittingportion. Since the material capable of revealing a high coefficient offriction is accumulated only in a contacting portion, it is possible toreveal various combinations of an oily medium with physical propertiesof the compound of the invention, and it is possible to inexpensivelyprovide a combination satisfying many requirements of a transmission.

3.-1 Viscosity-Pressure Modulus

The smaller the viscosity-pressure modulus of the compound representedby the foregoing formula (I), the smaller the viscosity under a highpressure is relatively. The viscosity-pressure modulus of the foregoingcompound at 40° C. is preferably not more than 20 GPa⁻¹, more preferablynot more than 15 GPa⁻¹, and especially preferably not more than 10GPa⁻¹. Though it is preferable that the viscosity-pressure modulus issmall as far as possible, it has been elucidated that theviscosity-pressure modulus is correlative to the free volume of themolecule, and it may be conjectured that a lower limit value of theviscosity-pressure modulus of the organic compound under the foregoingcondition is about 5 GPa⁻¹.

3.-2 Elementary Formulation:

The compound of the invention is preferably constituted of only carbon,hydrogen and oxygen. In general, the current lubricating oils containphosphorus, sulfur and a heavy metal. In a lubricating oil to be usedfor a 2-stroke engine of combusting the lubricating oil together with afuel, though it does not contain phosphorus and a heavy metal whiletaking into consideration the environmental load, it contains sulfur inan amount of about a half of a lubricating oil to be used for a 4-strokeengine. That is, in the current lubricating technologies, though it maybe conjectured that the formation of a boundary lubricating film made ofsulfur is essential at a minimum. In view of the fact that a sulfurelement is contained, a load to a catalyst for exhaust gas cleaning isvery large. In this catalyst for exhaust gas cleaning, though platinumand nickel are used, a poisoning action of phosphorus or sulfur is aserious problem. From this point of issue, a merit to be brought due tothe fact that elements constituting a composition of the lubricating oilare composed of only carbon, hydrogen, oxygen and nitrogen is verylarge. In addition, the fact that the composition is composed of onlycarbon, hydrogen and oxygen is optimal for lubricating oils ofindustrial machines, in particular food manufacturing-related devices.According to the current technology, an elementary composition takinginto consideration the environment while scarifying the coefficient offriction is adopted. This is also a very preferable technology for alubricating oil for cutting or working a metal requiring a large amountof water for cooling. In many cases, the lubricating oil inevitablyfloats or vaporizes in the air as a mist, and a treatment waste fluid isdischarged into the natural system. Therefore, in order to make both thelubricating properties and the environmental protection compatible witheach other, it is very preferable to substitute the current lubricatingoils with the composition of the invention which is constituted of onlycarbon, hydrogen and oxygen.

And not only lubricant oils but also any materials used in variousapplications are required to be an environmental harmony-type material,and the compound of the invention is fit for the purpose.

3.-3. Liquid Crystallinity:

The compound of the invention may be a liquid crystal compounds. Fromthe viewpoint of lubricating performance, it is preferable that thecompound of the invention exhibits liquid crystallinity. This is becausein view of the fact that the compound reveals liquid crystallinity, themolecule is oriented in the sliding portion, and a lower coefficient offriction is revealed due to an effect of its anisotropic low viscosity(see, for example, Ken KAWATA and Nobuyoshi OHNO, Fujifilm Research andDevelopment (No. 51-2006, pp. 80 to 85).

As for the liquid crystallinity, the compound of the invention maysingly reveal thermotropic liquid crystallinity, or it may revealthermotropic liquid crystallinity together with the oily medium.

4. Applications of Compound of the Invention

The compound of the invention can be used in various applications. Oneexample is a lubricant. The compound of the invention can be used aloneas a lubricant, or the embodiments of dispersion compositions or thelike, of which the compound of the invention is dispersed and/ordissolved in an oily or aqueous medium, can be used as a lubricant. Forexample, it is fed between the two sliding surfaces and can be used forreducing the friction. The compound of the invention or the compositioncontaining it is able to form a film on the sliding surface.

EXAMPLES

The invention is described in more detail with reference to thefollowing Examples. In the following Examples, the amount of thematerial, reagent and substance used, their ratio, the operation withthem and the like may be suitably modified or changed not oversteppingthe spirit and the scope of the invention. Accordingly, the scope of theinvention should not be limited to the following Examples.

1. Synthesis Examples of Illustrative Compounds 1-1. Synthesis Exampleof Illustrative Compound AII-2 Synthesis of 1-docosanyl methanesulfonate

247.4 g of behenyl alcohol (1-docosanol) was dissolved in 640 mL oftetrahydrofuran, 116.1 mL of methanesulfonyl chloride was graduallyadded, and 64.7 mL of triethylamine was then added dropwise under icecooling over 30 minutes. After stirring for one hour, the mixture washeated at 40° C. and further stirred for 30 minutes. The reactionmixture was poured into 3.5 L of ice water, and the resulting mixturewas ultrasonically dispersed for 15 minutes and further stirred at roomtemperature for 4 hours. The dispersion was filtered under reducedpressure, and a crystal was washed with 2 L of water. The resultingwhite crystal was stirred in 1.5 L of acetonitrile for one hour,filtered under reduced pressure and then washed with 0.5 L ofacetonitrile. The resulting crystal was dried under reduced pressure toobtain 303.4 g of a white crystal.

Synthesis of tetraethylene glycol mono-1-docosanyl ether

80.4 g of 1-docosanyl methanesulfonate was added to 207 mL oftetraethylene glycol, and the mixture was heated at 110° C. 40.0 g oft-butoxypotassium was gradually added over 2 hours. The mixture wasfurther stirred for 3 hours, and after cooling, the reaction mixture waspoured into 3 L of ice water, to which was then added 2 L of ethylacetate, the mixture was stirred, and 22.2 g of an insoluble matter wasfiltered. An ethyl acetate phase was extracted and separated from thefiltrate, after concentration under reduced pressure, 0.5 L ofacetonitrile was added, and the mixture was stirred under ice coolingfor one hour. The reaction mixture was filtered under reduced pressureand washed with 0.2 L of cold acetonitrile to obtain 81.6 g of a whitecrystal.

Synthesis of 3-(1-docosanyl tetraethyleneoxycarbonyl)propionic acid

25.0 g of tetraethylene glycol mono-1-docosanyl ether was dissolved in160 mL of toluene, to which were then added 7.5 g of succinic anhydrideand two drops of concentrated sulfuric acid, and the mixture was heatedat 125° C. for 8 hours. After cooling, 0.3 L of acetonitrile was added,and the mixture was stirred under ice cooling for one hour and thenfiltered under reduced pressure. The reaction mixture was washed with100 mL of cold acetonitrile and then dried under reduced pressure toobtain 23.3 g of a white crystal.

Synthesis of Illustrative Compound AII-2

5.0 g of 3-(1-docosanyl tetraethyleneoxycarbonyl)propionic acid wasdissolved in 20 mL of toluene, two drops of dimethylformamide and 2 mLof thienyl chloride were then added thereto. After 5 minutes, themixture was heated at 80° C. and further stirred for 2 hours, and aftercooling, toluene and excessive thienyl chloride were distilled off underreduced pressure. 15 mL of toluene and 283 mg of pentaerythritol wereadded thereto, and 5 mL of pyridine was then gradually added. Afterheating at 80° C. for 8 hours, the reaction mixture was cooled, 200 mLof methanol was poured thereinto, and the mixture was stirred for 2hours. The reaction mixture was filtered under reduced pressure toobtain 4.8 g of a white crystal.

1-2. Synthesis Example of Illustrative Compound AII-5

Illustrative Compound AII-5 was synthesized in the same manner, exceptfor replacing 1-docosanol as the starting raw material of IllustrativeCompound II-2 with 1-stearyl alcohol.

1-3. Synthesis Example of Illustrative Compound AII-8

Illustrative Compound AII-8 was synthesized in the same manner, exceptfor replacing 1-docosanol as the starting raw material of IllustrativeCompound AII-2 with 1-tetradecanol.

1-4. Synthesis Example of Illustrative Compound AII-1 Synthesis of3-(1-docosanyl polyethyleneoxycarbonyl)propionic acid

25.6 g of polyethylene glycol mono-1-docosanyl ether (manufactured byTakemoto Oil & Fat Co., Ltd.; average degree of polymerization ofethyleneoxy group: 6.65) was dissolved in 160 mL of toluene, to whichwere then added 8.0 g of succinic anhydride and two drops ofconcentrated sulfuric acid, and the mixture was heated at 125° C. for 8hours. After cooling, 0.3 L of acetonitrile was added, and the mixturewas stirred under ice cooling for one hour and then filtered underreduced pressure. The reaction mixture was washed with 100 mL of coldacetonitrile and then dried under reduced pressure to obtain 22.3 g of awhite crystal.

Synthesis of Illustrative Compound AII-1

5.18 g of 3-(1-docosanyl polyethyleneoxycarbonyl)propionic acid wasdissolved in 10 mL of toluene, and two drops of dimethylformamide and 2mL of thienyl chloride were then added thereto. After 5 minutes, themixture was heated at 80° C. and further stirred for 2 hours, and aftercooling, toluene and excessive thienyl chloride were distilled off underreduced pressure. 14 mL of toluene and 245 mg of pentaerythritol wereadded thereto, and 6 mL of pyridine was then added thereto. Afterheating at 80° C. for 8 hours, the reaction mixture was cooled, 200 mLof methanol was poured thereinto, and the mixture was stirred for 2hours. The reaction mixture was filtered under reduced pressure toobtain 4.69 g of a white crystal.

1-5. Synthesis Example of Illustrative Compound AII-17

Illustrative Compound AII-17 was synthesized in the same manner, exceptfor changing the average degree of polymerization of 6.65 ofpolyethylene glycol mono-1-dosanyl ether as the starting raw material ofIllustrative Compound AII-1 to an average degree of polymerization of10.30.

1-6. Synthesis Example of Illustrative Compound AII-18

Illustrative Compound AII-18 was synthesized in the same manner, exceptfor changing the average degree of polymerization of 6.65 ofpolyethylene glycol mono-1-dosanyl ether as the starting raw material ofIllustrative Compound AII-1 to an average degree of polymerization of19.0.

1-7. Synthesis Example of Illustrative Compound AII-33

Illustrative Compound AII-33 was synthesized in the same manner, exceptfor replacing succinic anhydride used in Illustrative Compound AII-1with Meldrum's acid.

1-8. Synthesis Example of Illustrative Compound AII-34

Illustrative Compound AII-34 was synthesized in the same manner, exceptfor replacing succinic anhydride used in Illustrative Compound AII-1with glutaric anhydride.

1-9. Synthesis Example of Illustrative Compound AII-36

Illustrative Compound AII-36 was synthesized in the same manner, exceptfor replacing succinic anhydride used in Illustrative Compound AII-1with maleic anhydride.

1-10. Synthesis Example of Illustrative Compound AII-37

Illustrative Compound AII-37 was synthesized in the same manner, exceptfor replacing succinic anhydride used in Illustrative Compound AII-1with diglycolic anhydride.

1-11. Synthesis Example of Illustrative Compound AII-38

Illustrative Compound AII-38 was synthesized in the same manner, exceptfor replacing succinic anhydride used in Illustrative Compound AII-1with phthalic anhydride.

1-12. Synthesis Example of Illustrative Compound AII-40

Illustrative Compound AII-40 was synthesized in the same manner, exceptfor replacing succinic anhydride used in Illustrative Compound AII-1with 3,3-dimethylglutaric anhydride.

Various illustrative compounds were prepared in the similar manner asthe above. Regarding some of them, their NMR spectra data, IR data andmelting point are shown below.

Illustrative Compound AII-1:

¹H NMR (400 MHz, CDCl₃): δ4.24 (8H, t), 4.13 (8H, s), 3.65 (64H, m),3.44 (8H, t), 2.64 (16H, dd), 1.58 (16H, t), 1.25 (160H, br), 0.88 (12H,t).

IR data (neat) cm⁻¹: 2924(s), 2853(s), 1739(s), 1465(s), 1350(s),1146(s), 720(m).

Melting point: 63.5-64.0 degrees Celsius.

Illustrative Compound AII-2:

¹H NMR (300 MHz, CDCl₃): δ4.24 (8H, t), 4.13 (8H, s), 3.65 (64H, m),3.44 (8H, t), 2.65 (12H, br), 1.57 (8H, t), 1.25 (160H, br), 0.88 (12H,t).

IR data (neat) cm⁻¹: 2927(s), 2854(s), 1741(s), 1464(s), 1350(m),1146(s), 720(w).

Melting point: 64.7-65.2 degrees Celsius

Illustrative Compound AII-3:

¹H NMR (400 MHz, CDCl₃): δ4.24 (8H, t), 4.13 (8H, s), 3.65 (72H, m),3.44 (8H, t), 2.64 (16H, m), 1.57 (16H, t), 1.26 (144H, br), 0.88 (12H,t).

IR data (neat) cm⁻¹: (neat): 2924(s), 2852(s), 1738(s), 1465(s),1350(s), 1140(b), 858(m), 720(m).

Melting point: 55.1-55.6 degrees Celsius

Illustrative Compound AII-4:

¹H NMR (400 MHz, CDCl₃): δ4.24 (8H, t), 4.13 (8H, s), 3.65 (64H, m),3.44 (8H, t), 2.63 (16H, m), 1.57 (8H, t), 1.25 (128H, br), 0.88 (12H,t).

IR data (neat) cm⁻¹: 2932(s), 2859 (s), 1746(s), 1465(s), 1350(s),1156(b), 856(m), 720(w).

Melting point: 46.0-47.0 degrees Celsius

Illustrative Compound AII-5:

¹H NMR (400 MHz, CDCl₃): δ4.24 (8H, t), 4.13 (8H, s), 3.65 (64H, m),3.44 (8H, t), 2.64 (16H, s), 1.57 (16H, t), 1.25 (120H, br), 0.88 (12H,t).

IR data (neat) cm⁻¹: 2924(s), 2853(s), 1740(s), 1464(s), 1350(s),1144(s), 718(m).

Melting point: 47.0-47.8 degrees Celsius

Illustrative Compound AII-6:

¹H NMR (300 MHz, CDCl₃): δ4.24 (8H, t), 4.13 (8H, s), 3.65 (80H, m),3.44 (8H, t), 2.64 (16H, d), 1.57 (16H, br), 1.25 (120H, br), 0.88 (12H,t).

IR data (neat) cm⁻¹: 2920(s), 2852(s), 1737(s), 1458(s), 1350(s),1105(b), 862(m), 719(m).

Melting point: 35.3-35.8 degrees Celsius

Illustrative Compound AII-7:

¹H NMR (300 MHz, CDCl₃): δ4.24 (8H, br), 4.13 (8H, s), 3.65 (80H, m),3.44 (8H, t), 2.64 (16H, s), 1.57 (8H, br), 1.26 (96H, br), 0.88 (12H,t).

IR data (neat) cm⁻¹: 2925(s), 2854(s), 1740(s), 1465(m), 1350(m),1253(s), 1147(s).

Melting point: oil at a room temperature

Illustrative Compound AII-8:

¹H NMR (300 MHz, CDCl₃): δ4.24 (8H, t), 4.13 (8H, s), 3.65 (60H, m),3.44 (8H, t), 2.64 (16H, s), 1.59 (40H, br), 1.26 (96H, m), 0.88 (12H,t).

IR data (neat) cm⁻¹: 2927(s), 2855(s), 1740(s), 1465(m), 1350(m),1252(s), 1152(s), 1038(m), 859(w).

Melting point: 39.5-40.5 degrees Celsius

Illustrative Compound AII-14:

¹H NMR (300 MHz, CDCl₃): δ4.24 (8H, t), 4.13 (8H, s), 3.65 (64H, m),3.44 (8H, t), 2.64 (16H, m), 1.57 (8H, t), 1.25 (160H, br), 0.88 (12H,t).

IR data (neat) cm⁻¹: 2928(s), 2854(s), 1742(s), 1465(m), 1351(s),1250(s), 1150(s), 720(w).

Melting point: 63.6-64.4 degrees Celsius

Illustrative Compound AII-15:

¹H NMR (400 MHz, CDCl₃): δ4.24 (8H, t), 4.13 (8H, s), 3.65 (104H, m),3.44 (8H, t), 2.64 (16H, m), 1.57 (8H, t), 1.25 (168H, br), 0.88 (12H,t).

IR data (neat) cm⁻¹: 2925(s), 2853(s), 1740(s), 1465(s), 1350(s),1147(b), 865(m), 720(m).

Melting point: 61.9-62.9 degrees Celsius

Illustrative Compound AII-16:

¹H NMR (300 MHz, CDCl₃): δ4.24 (8H, t), 4.13 (8H, s), 3.65 (120H, m),3.44 (8H, t), 2.64 (16H, s), 1.57 (8H, br), 1.25 (160H, br), 0.88 (12H,t).

IR data (neat) cm⁻¹: 2925(s), 2854(s), 2361(w), 1740(s), 1558(w),1457(w), 1250(s), 1146(b).

Melting point: 59.3-60.3 degrees Celsius

Illustrative Compound AII-17:

¹H NMR (400 MHz, CDCl₃): δ4.23 (8H, t), 4.13 (8H, s), 3.64 (144H, m),3.57 (8H, m), 3.44 (8H, t), 2.64 (16H, m), 1.57 (8H, t), 1.25 (160H,br), 0.88 (12H, t).

IR data (neat) cm⁻¹: 2925(s), 2854(s), 1741(s), 1465(m), 1351(w),1144(s).

Melting point: 55.6-56.3 degrees Celsius

Illustrative Compound AII-18:

¹H NMR (300 MHz, CDCl₃): δ4.24 (8H, t), 4.13 (8H, s), 3.64 (288H, m),3.44 (8H, t), 2.64 (16H, m), 1.59 (32H, br), 1.25 (160H, br), 0.88 (12H,t).

IR data (neat) cm⁻¹: 2924(s), 2854(s), 1738(s), 1459(s), 1349(s),1250(s), 1109(b), 857(m).

Melting point: 43.8-47.1 degrees Celsius

Illustrative Compound AII-19:

¹H NMR (300 MHz, CDCl₃): δ4.24 (8H, t), 4.13 (8H, s), 3.64 (424H, m),3.44 (16H, t), 2.64 (16H, m), 1.59 (40H, br), 1.25 (160H, br), 0.88(12H, t).

IR data (neat) cm⁻¹: 2925(s), 2856(s), 1739(s), 1460(m), 1350(s),1296(s), 1251(s), 1119(b), 946(m), 857(m).

Melting point: 46.4-47.4 degrees Celsius

Illustrative Compound AII-33:

¹H NMR (400 MHz, CDCl₃): δ4.30 (8H, t), 4.21 (8H, s), 3.65 (72H, m),3.45 (16H, m), 3.24 (8H, t), 1.57 (8H, t), 1.25 (160H, br), 0.88 (12H,t).

IR data (neat) cm⁻¹: 3481(b), 2924(s), 2853(s), 1739(s), 1648(m),1559(w), 1465(s), 1266(b), 1129(b), 1041(s), 720(m).

Melting point: 65.5-66.5 degrees Celsius

Illustrative Compound AII-34:

¹H NMR (400 MHz, CDCl₃): δ4.23 (8H, m), 4.11 (8H, s), 3.65 (80H, m),3.44 (8H, t), 2.41 (16H, t), 1.96 (8H, tt), 1.59 (8H, br), 1.25 (160H,br), 0.88 (12H, t).

IR data (neat) cm⁻¹: 3495 (b), 2930(s), 2855(s), 1740(s), 1464(s),1351(m), 1136(s), 720(w).

Melting point: 59.9-61.6 degrees Celsius

Illustrative Compound AII-36:

¹H NMR (300 MHz, CDCl₃): δ6.88 (4H, d), 6.84 (4H, d), 4.33 (16H, m),3.64 (64H, m), 3.44 (16H, t), 1.57 (8H, br), 1.25 (160H, m), 0.88 (12H,t).

IR data (neat) cm⁻¹: 2923(s), 2853(s), 1728(s), 1465(s), 1351(m),1292(s), 1254(s), 1146(s), 769(s), 720(m).

Melting point: 60.2-61.5 degrees Celsius

Illustrative Compound AII-37:

¹H NMR (300 MHz, CDCl₃): δ4.32 (8H, t), 4.27 (16H, s), 4.23 (8H, s),3.72 (8H, m), 3.65 (80H, m), 3.44 (8H, t), 1.57 (8H, br), 1.25 (160H,br), 0.88 (12H, t).

IR data (neat) cm⁻¹: 2926(s), 2854(s), 1758(s), 1465(s), 1351(m),1204(s), 1138(s), 720(m).

Melting point: 60.6-63.8 degrees Celsius

Illustrative Compound AII-38:

¹H NMR (300 MHz, CDCl₃): δ7.74 (8H, m), 7.54 (8H, m), 4.46 (8H, t), 3.91(8H, s), 3.80 (8H, t), 3.64 (80H, m), 3.44 (8H, t), 1.64 (16H, br), 1.25(152H, m), 0.88 (12H, t).

IR data (neat) cm⁻¹: 2925(s), 2854(s), 1733(s), 1465(w), 1287(s),1122(s), 743(w).

Melting point: 64.7-65.7 degrees Celsius

Illustrative Compound AII-40:

¹H NMR (400 MHz, CDCl₃): δ4.22 (8H, m), 4.09 (8H, s), 3.64 (72H, m),3.44 (8H, t), 2.43 (8H, t), 1.56 (8H, br), 1.25 (160H, m), 1.09 (24H,s), 0.88 (12H, t)

IR data (neat) cm⁻¹: 2924(s), 2853(s), 1737(m), 1465(m), 1287(m),1123(s).

Melting point: 53.1-53.7 degrees Celsius

Illustrative Compound AII-41:

¹H NMR (300 MHz, CDCl₃): δ4.50 (8H, s), 4.35 (8H, t), 3.67 (96H, m),3.48 (8H, m), 1.58 (8H, br), 1.25 (160H, m), 0.88 (12H, t).

IR data (neat) cm⁻¹: 2927(s), 2855(s), 1780(s), 1465(m), 1246(m),1178(s), 942(m).

Melting point: 56.2-57.0 degrees Celsius

Illustrative Compound AII-43:

¹H NMR (300 MHz, CDCl₃): δ4.52 (8H, s), 4.46 (8H, t), 3.77 (8H, t), 3.64(64H, m), 3.44 (8H, t), 1.74 (16H, br), 1.56 (8H, t), 1.25 (160H, m),0.88 (12H, t).

IR data (neat) cm⁻¹: 2925(s), 2853(s), 1747(m), 1631(m), 1519(s),1479(s), 1396(s), 1323(s), 1214(b), 1119(s), 721(m).

Melting point: 55.4-56.4 degrees Celsius

Illustrative Compound AII-65:

¹H NMR (400 MHz, CDCl₃): δ4.24 (8H, t), 4.14 (8H, s), 3.64 (88H, m),3.56 (8H, t), 3.32 (8H, d), 2.64 (16H, d), 1.59 (40H, br), 1.26 (84H,br), 0.85 (76H, m), 0.75 (12H, t).

IR data (neat) cm⁻¹: 2955(s), 2926(s), 2858(s), 1737(s), 1460(s),1378(s), 1349(s), 1248(s), 1105(s), 1038(s), 861(m).

Melting point: oil at a room temperature

Illustrative Compound AII-88:

¹H NMR (400 MHz, CDCl₃): δ4.24 (8H, t), 4.14 (8H, s), 3.64 (88H, m),3.56 (8H, t), 3.32 (8H, d), 2.64 (16H, d), 1.59 (40H, br), 1.26 (84H,br), 0.85 (76H, m), 0.75 (12H, t).

IR data (neat) cm⁻¹: 2955(s), 2926(s), 2858(s), 1737(s), 1460(s),1378(s), 1349(s), 1248(s), 1105(s), 1038(s), 861(m).

Melting point: oil at a room temperature

Illustrative Compound AII-89:

¹H NMR (400 MHz, CDCl₃): δ4.24 (8H, t), 4.14 (8H, s), 3.64 (88H, m),3.56 (8H, t), 3.32 (8H, d), 2.64 (16H, d), 1.59 (40H, br), 1.26 (84H,br), 0.85 (76H, m), 0.75 (12H, t).

IR data (neat) cm⁻¹: 2955(s), 2926(s), 2858(s), 1737(s), 1460(s),1378(s), 1349(s), 1248(s), 1105(s), 1038(s), 861(m).

Melting point: oil at a room temperature

Illustrative Compound AII-90:

¹H NMR (400 MHz, CDCl₃): δ4.24 (8H, t), 4.14 (8H, s), 3.64 (88H, m),3.56 (8H, t), 3.32 (8H, d), 2.64 (16H, d), 1.59 (40H, br), 1.26 (84H,br), 0.85 (76H, m), 0.75 (12H, t).

IR data (neat) cm⁻¹: 2955(s), 2926(s), 2858(s), 1737(s), 1460(s),1378(s), 1349(s), 1248(s), 1105(s), 1038(s), 861(m).

Melting point: oil at a room temperature

2. Test Example 1 Evaluation of Compound

As for the Illustrative Compounds and Comparative Compounds, alubricating characteristic was evaluated using Optimol's reciprocatingfriction and wear tester (SRV) under the following condition.

Evaluation and Measurement Methods by Reciprocating (SRV) Friction andWear Test:

A coefficient of friction was evaluated using a reciprocating (SRV)friction and wear tester under the following test condition.

-   -   Test piece (friction material): SUJ-2    -   Plate: 24 mm in diameter×7 mm in thickness, surface roughness:        0.45 to 0.65 μm    -   Cylinder: 15 mm in diameter×22 mm in width, surface roughness:        up to 0.05 μm    -   Temperature: 30 to 150° C.    -   Load: 50 N, 75 N, 100 N, 200 N and 400 N    -   Amplitude: 1.5 mm    -   Frequency: 50 Hz    -   Time change pattern of temperature and load

The temperature was initially set up at 90° C., and after keeping for acertain period of time, it was dropped to the neighborhood of a meltingpoint of each raw material by 10° C. at intervals of ten minutes.Thereafter, the temperature was similarly increased to 150° C. andfurther dropped to 50° C.

The pressure (load) was changed in a manner of 50 N→75 N→100 N→200 N→400N→50 N at intervals of one minute twice at 90° C. and once at 120° C.and 150° C., respectively.

The illustrative compounds used for the evaluation are AII-1, 2, 17, 18and 65. Moreover, as the comparative compounds, alkyleneoxy group-freepentaerythritol tetrastearate (C(CH₂OCOC₁₇H₃₅-n)₄: Comparative CompoundC-1) and C{CH₂O(C₂H₄O)_(6.5)C₂₂H₄₅-n}₂ (Comparative Compound C-2), theboth of which are a compound generally used as a lubricant, were used,respectively.

The measurement results are shown in FIGS. 1 to 4.

On review of the measurement results shown in FIGS. 1 to 4, it can beunderstood that Illustrative Compounds AII-1, AII-2, AII-17, AII-18 andAII-65 are conspicuously small in the coefficient of friction ascompared with Comparative Compounds C-1 and C-2.

It is noted that in all of Illustrative Compounds AII-1, AII-2, AII-17,AII-18 and AII-65 of the formula (Z), the coefficient of frictionabruptly increases in the vicinity of the melting point at the time offirst temperature drop. It may be conjectured that this is an increaseof the coefficient of friction to be caused due to an abrupt increase ofthe viscosity getting close to the melting point. Moreover, it may beconsidered that in view of the fact that the coefficient of frictiondoes not depend upon a change of the viscosity so much in the subsequenttemperature increase and temperature drop processes, the material is ina fluid lubricating state in a low temperature region in the vicinity ofthe melting point, whereas it is an elastic fluid lubrication region ata temperature higher than that temperature.

On the other hand, in all of Comparative Compounds C-1 and C-2, themelting point is not higher than 60° C., an increase of the coefficientof friction is seen in the vicinity thereof, and the coefficient offriction is not influenced by a change of the temperature at atemperature higher than that temperature. It may be considered thatthese compounds undergo frictional sliding in a region of from fluidlubrication to elastic fluid lubrication similarly to the foregoingillustrative compounds.

In Illustrative Compound AII-65 having the lowest viscosity among thesecompounds, it can be understood that the coefficient of frictionexhibits distinct positive temperature dependency, and it may beconsidered from the Stribeck curve that it is suggested that AII-65relatively contributes to mixed lubrication.

Since all of other compounds than Illustrative Compound AII-65 exhibit asimilar melting point, it is safe to consider that the viscosity ofthese compounds is also similar. So, in view of the fact that thecoefficients of friction of Illustrative Compounds AII-1, AII-2, AII-17,AII-18 and AII-65 are conspicuously different from the coefficients offriction of Comparative Compounds C-1 and C-2, it may be considered fromthe Barus equation: η=η₀exp(αP), which expresses the pressure dependencyof viscosity, there is a significant difference in the viscosity η undera high pressure P in an elastic fluid lubrication region, namely aviscosity-pressure modulus α. This is one of the characteristic featuresof the group of compounds of the invention.

Moreover, results obtained by evaluating a wear depth of the slidingpart of the test piece after the frictional sliding test of each of thecompounds using a laser microscope are shown below.

TABLE 1 Compound No. Wear Depth [μm] Illustrative Compound AII-1 0.07Illustrative Compound AII-2 0.05 Illustrative Compound AII-17 0.03Illustrative Compound AII-18 0.02 Illustrative Compound AII-65 0.08Compound C-1 for comparative Example 0.25 Compound C-2 for comparativeExample 0.32

The following can be understood from the results shown in the table.

When the illustrative compounds of the formula (Z) were utilized, thewear depth was extremely shallow, and a sliding scar itself was notsubstantially observed. On the other hand, when the comparativecompounds were utilized, a distinct sliding scar was observed in all ofthe cases. That is, as for the wear depth, there was generated adistinct difference between the illustrative compounds and thecomparative compounds.

3. Test Example 2 Evaluation of Oily Medium Dispersion Composition

As for the compositions of the invention and the comparativecompositions, a lubricating characteristic was evaluated using Optimol'sreciprocating friction and wear tester (SRV) under the followingcondition.

Evaluation and Measurement Methods by Reciprocating (SRV) Friction andWear Test:

A coefficient of friction and wear resistance were evaluated using areciprocating (SRV) friction and wear tester, and a friction and weartest was carried out under the following test condition.

-   -   Lubricant composition:

SUPER OIL N-32 (manufactured by Nippon Oil Corporation) which is amineral oil was used as an oily medium, to which was then addedIllustrative Compound AII-1 in a concentration of 1.0% by mass; themixture was heated to 70° C. to form a transparent solution; and afterair cooling for 10 minutes, this composition was tested under thefollowing condition. This composition became cloudy step-by-step at thetime of air cooling.

-   -   Test piece (friction material): SUJ-2    -   Plate: 24 mm in diameter×7 mm in thickness, surface roughness:        0.45 to 0.65 μm    -   Cylinder: 15 mm in diameter×22 mm in width, surface roughness:        up to 0.05 μm    -   Temperature: 25 to 110° C.    -   Load: 50 N, 75 N, 100 N, 200 N and 400 N    -   Amplitude: 1.5 mm    -   Frequency: 50 Hz    -   Test method:

About 60 mg of the sample composition was placed in a portion where thecylinder slid on the plate and subjected to frictional sliding accordingto the following steps, thereby evaluating a coefficient of friction ateach temperature and each load, and the following steps were repeateduntil a substantially constant pattern was obtained. After thecompletion, a wear depth of the plate was evaluated by a lasermicroscope.

Similarly, SUPER OIL N-32 (manufactured by Nippon Oil Corporation) whichis a mineral oil was used as an oily medium, to which was then addedeach of the following illustrative compounds in a concentration of 1.0%by mass in place of Illustrative Compound AII-1, thereby evaluating thedependency of the coefficient of friction on temperature, pressure andlapsing time. Among the test sample compositions, as for samplecompositions prepared using each of Illustrative Compounds AII-1, 3, 4,5, 6, 7, 8, 14, 16, 17, 18, 19, 33, 34, 36, 37, 38, 40, 41, 42, 43, 65,88, 89 and 90, the results are shown in respective graphs shown in FIGS.5 to 17.

Moreover, compositions were similarly prepared using, as a comparativecompound, each of compounds which are a pentaerythritol derivative butdo not contain a polyalkyleneoxy group, specifically ComparativeCompound C-3 (C(CH₂OCOC₂H₄CO₂C₂₂H₄₅-n)₄) and Comparative Compound C-6(C(CH₂OCOC₁₇H₃₅-n)₄) and tested. The rest results are shown in a graphshown in FIG. 18.

Moreover, as a referential example, only SUPER OIL N-32 used as an oilymedium, which is a mineral oil, was similarly tested. The results areshown in a graph shown in FIG. 19.

As shown in FIG. 5, it can be understood that the sample preparedutilizing Illustrative Compound AII-1 exhibits a low friction offriction such that the coefficient of friction at 25° C. is not morethan 0.05. As shown in FIG. 1, since Illustrative Compound AII-1 issingly a crystal having a melting point of from 63.5 to 64.0° C., itscoefficient of friction of SRV at 25° C. was 0.3 or more because of itshigh viscosity. Moreover, as shown in FIG. 19, SUPER OIL N-32 used as anoily medium, which is a mineral oil, singly exhibits a coefficient offriction at 25° C. of 0.07 or more. From this fact, it may be consideredthat in a state where Illustrative Compound AII-1 is dispersed in aconcentration of 1.0% by mass in SUPER OIL N-32, the both do not worksingly but mutually work as some kind of interaction, thereby revealingthis small coefficient of friction.

In general, if a low-viscosity fluid and a high-viscosity fluid arepresent in the vicinity of an interface and produce a high shear field,the matter that the high-viscosity fluid forms a smooth coating film byshear in the vicinity of the harder interface, and the low-viscosityfluid is interposed in a gap between the both interfaces, therebyrevealing a lower coefficient of friction conforms with the reason oflubrication, and it is suggested that such a phenomenon occurs.

In the sample containing Illustrative Compound AII-1, the coefficient offriction abruptly increases to 0.09 with an increase of the temperature,and that coefficient of friction is kept in the range of from 60 to 110°C. without utterly depending upon the temperature. It may be supposedthat this is caused due to the fact that this lubrication state residesin elastic fluid lubrication but not boundary lubrication. This isbecause as shown in FIG. 19, the coefficient of friction of SUPER OILN-32 which is a fluid with lower viscosity exhibits distinct positivetemperature dependency, and it is strongly suggested that SUPER OIL N-32slides in a mixed lubrication region; and therefore, it is hardlyconsidered that SUPER OIL N-32 abruptly comes into the boundarylubrication in a field where a fluid with higher viscosity coexists.

As shown in FIGS. 5 to 17, as for the samples prepared utilizing otherillustrative compounds, the same behavior as that in IllustrativeCompound AII-1 was observed.

On the other hand, it can be understood that all of the compositionsprepared utilizing Comparative Compounds C-3 and C-6, respectively arehigh in the coefficient of friction as compared by the compositionsprepared utilizing each of the illustrative compounds.

A measurement value of a wear scar depth of the sliding part of each ofthe samples after the frictional sliding test is shown below. In thisconnection, Comparative Compound C-4 is C{CH₂O(C₂H₄O)_(6.5)C₂₂H₄₅-n}₂.

TABLE 2 Wear Depth Material No. [μm] AI-1 0.33 AI-2 0.25 AI-3 0.23 AI-40.14 AI-5 0.13 AI-6 0.28 AI-7 0.45 AI-8 0.22 AI-12 0.18 AI-15 0.09 AI-220.34 AI-26 0.28 AI-30 0.41 AI-32 0.33 AI-34 0.25 AI-55 0.24 AI-58 0.14AI-68 0.53 AI-71 0.15 AI-76 0.20 AII-1 0.08 AII-2 0.13 AII-3 0.13 AII-40.09 AII-5 0.07 AII-6 0.08 AII-7 0.14 AII-8 0.07 AII-15 0.25 AII-16 0.14AII-17 0.06 AII-18 0.07 AII-19 0.12 AII-21 0.21 AII-23 0.09 AII-24 0.16AII-33 0.11 AII-34 0.13 AII-35 0.23 AII-36 0.22 AII-37 0.12 AII-38 0.11AII-39 0.07 AII-40 0.11 AII-41 0.13 AII-42 0.10 AII-43 0.19 AII-48 0.14AII-49 0.32 AII-50 0.22 AII-54 0.23 AII-57 0.24 AII-59 0.33 AII-60 0.23AII-64 0.22 AII-65 0.14 AIII-1 0.09 AIII-2 0.09 AIII-7 0.21 Comparative0.69 Example C-3 Comparative 0.98 Example C-4 Comparative 1.23 ExampleC-6 Mineral Oil 1.07 (N-32)

It can be understood that the samples of the Examples containing thecompound of the invention are markedly shallow in the wear scar andexcellent in the wear resistance as compared with those of theComparative Examples.

In this connection, as compared with the wear scar depths of TestExample 1, the results of Test Example 2 generally exhibit large values.That appears to be very natural because in Test Example 2, the compoundis used singly for the sample so that elastic fluid lubrication in anapproximately thick film thickness is revealed, whereas in the presenttest example, only 1% by mass of the compound is contained in SUPER OILN-32 as a low-viscosity oil. In addition, since the foregoing resultsinclude an example giving the same results as those obtained under thenon-dilution condition of Test Example 1, it can be understood that thecompositions of the Examples of the invention also have excellentproperties regarding the wear resistance.

4. Test Example 3

Compositions were similarly prepared by using each of a commerciallyavailable poly-α-olefin (manufactured by Nippon Oil Corporation), apolyol ester (POE), a commercially available fluid andN-methylpyrrolidone as the oily medium in place of SUPER OIL N-32 whichis a mineral oil and adding Illustrative Compound AII-4 in aconcentration of 1.0% by mass thereto and then evaluated for thedependency of the coefficient of friction on temperature, pressure andlapsing time in the same manner as in Test Example 2. The results areshown in respective graphs shown in FIGS. 20 to 21.

From the results shown in FIGS. 20 to 21, it can be understood that evencompositions prepared using any material as the oily medium exhibit alow coefficient of friction.

5. Test Example 4

A reciprocating (SRV) friction and wear test was carried out under thefollowing condition. However, the evaluation was conducted onpolyetheretherketone as a resin and aluminum oxide as a ceramic as otherraw material than steel. A coefficient of friction and wear resistancewere evaluated using a reciprocating (SRV) friction and wear tester, anda friction and wear test was carried out under the following testcondition.

Preparation of Sample

SUPER OIL N-32 (manufactured by Nippon Oil Corporation) which is amineral oil was used as a base oil, to which was then added IllustrativeCompound AII-1 in a concentration of 1.0% by mass, and the mixture washeated to 70° C. to form a transparent solution, followed by air coolingfor 10 minutes, thereby obtaining a dispersion composition for sample.This sample became cloudy step-by-step at the time of air cooling.

Test Condition:

The above-prepared sample was tested under the following condition.

-   -   Test piece (friction material): SUJ-2    -   Cylinder: 15 mm in diameter×22 mm in width, surface roughness:        up to 0.05 μm    -   Plate: 24 mm in diameter×7 mm in thickness, surface roughness:        0.45 to 0.65 μm    -   Temperature: 30 to 180° C.    -   Load: 50 N, 75 N, 100 N, 200 N and 400 N    -   Amplitude: 1.5 mm    -   Frequency: 50 Hz

Test Method:

About 60 mg of the foregoing sample was placed in a portion where thecylinder slid on the plate and subjected to frictional sliding accordingto the following steps, thereby evaluating a coefficient of friction ateach temperature and each load.

(1) A coefficient of friction with time is measured until a fluctuationof a value of the coefficient of friction at 30° C. under 50 N for 10minutes becomes not more than 0.01.(2) The sample is heated under 50 N by increasing the temperature from30° C. to 110° C. at intervals of 10° C., thereby measuring acoefficient of friction at each temperature.(3) The same is cooled to 30° C.(4) (30 minutes after starting the cooling), a coefficient of frictionis measured at 30° C. under 50 N, 75 N, 100 N, 200 N and 400 N,respectively.(5) The sample is heated by increasing the temperature from 30° C. to110° C. at intervals of 10° C., thereby measuring a coefficient offriction at each temperature.However, a coefficient of friction is measured at each of 60° C. and 90°C. under 50 N, 75 N, 100 N, 200 N and 400 N, respectively.(6) (3) to (6) are repeated until a difference of the coefficient offriction at 70° C. or higher from the last is not substantially found.(7) The sample is cooled to 30° C.(8) (30 minutes after starting the cooling), the temperature isincreased from 30° C. to 180° C. at intervals of 10° C., therebymeasuring a coefficient of friction at each temperature.

However, a coefficient of friction is measured at each of 60° C., 90°C., 120° C., 150° C. and 180° C. under 50 N, 75 N, 100 N, 200 N and 400N, respectively.

(9) (5) and (6) are conducted, thereby finishing the operations.

The dependency of the coefficient of friction on temperature andpressure having become constant was evaluated with respect to each of aplate made of steel (SUJ-2), a plate obtained by forming a DLC thin filmon steel by a CVD method, a plate made of polyetheretherketone and aplate made of aluminum oxide.

-   -   Plate 1: 24 mm in diameter×7 mm in thickness, material quality:        diamond-like carbon, film thickness: 35 nm, surface roughness:        not more than 0.01 μm    -   Plate 2: 24 mm in diameter×7 mm in thickness, material quality:        polyetheretherketone, surface roughness: up to than 0.05 μm    -   Plate 3: 24 mm in diameter×7 mm in thickness, material quality:        aluminum oxide, surface roughness: up to than 0.15 μm

The results of the foregoing test are shown in FIG. 22. From the resultsshown in FIG. 22, it can be understood that the coefficient of frictionincreases in the order of DLC (diamond-like carbon)<PEEK<Fe(SUJ-2)<aluminum oxide at a low temperature. However, in this region,the film of Illustrative Compound AII-1 is much more hard, so that itmay be conjectured that the mineral oil N-32 used as a base oil revealsfluid lubrication in a gap relative to the thin film of IllustrativeCompound AII-1. If this conjecture is agreeable, it may be consideredthat this difference in the coefficient of friction is one reflectingthe film thickness of the fluid film of the mineral oil N-32 to becaused by Illustrative Compound AII-1 existing on the interface, in itsturn, the surface roughness of a base thereof. From a region where thetemperature exceeds 100° C., a lowering of the coefficient of frictionof each of the SUJ-2 and aluminum oxide plates is seen. However, in thisregion, Illustrative Compound AII-1 is in an elastic fluid lubricationregion, and it may be conjectured that an influence of the surfaceroughness of the interface base is also revealed here together with theeffect of elastic deformation. The diamond-like carbon coating film wasseparated on the way because the adhesion to steel was not sufficient.However, it is evident that all of the samples give a low coefficient offriction as compared with that obtained using the current lubricationtechnologies.

6. Test Example 5

As for a phenomenon in which Illustrative Compound AII-1 of theinvention is segregated in the sliding part, the present inventorspectrally observed a neighborhood of a point-contacting portion of aninstrument using a point contact EHL evaluation apparatus for evaluatingan elastic fluid lubrication region in the technical field of tribologyand succeeded in quantitatively grasping a change of materialconcentration at a high load in a high shear field. Specifically, theobservation was carried out in the following manner.

Preparation of Sample

First of all, Illustrative Compound AII-1 was dispersed in an oilymedium to prepare a sample. SUPER OIL N-32 (manufactured by Nippon OilCorporation) which is a mineral oil was used as the oily medium, towhich was then added Illustrative Compound AII-1 in a concentration of1.0% by mass, and the mixture was heated to 70° C. to form a transparentsolution, followed by air cooling for 10 minutes, thereby obtaining adispersion composition for sample. Thereafter, this sample was testedunder the following condition. In this connection, this sample becamecloudy step-by-step at the time of air cooling.

Outline of Measurement Method:

FIG. 23 is a diagrammatic view of an apparatus used for thismeasurement. For micro FT-IR, MICRO20 connected to FT-IR400,manufactured by JASCO Corporation was used, and the apparatus waspositioned such that the point-contacting portion of the point contactEHL evaluation apparatus was located in a working distance of aCassegrain mirror thereof. A rotating steel ball was placed on a diamond(hard plane) plate while making its rotation axis parallel, and a loadwas applied to the axis, thereby bringing them into press contact witheach other. The prepared sample was fed and flown in a gap between therotating steel ball and the diamond plate and its neighborhood.

Though a Newtonian ring which is an optical interference pattern isformed in a portion where the steel ball comes into point contact withthe diamond plate, by irradiating infrared rays from the opposite sideto the steel ball via the diamond plate and reflecting them on the steelball, an IR spectrum of a thin film of the sample in the vicinity of theNewtonian ring can be measured. FIG. 24 shows a figure of the Newtonianring formed by the point contact. A size of the Newtonian ring shown inFIG. 24 is about 200 μm, and a portion surrounded by a dotted line is anIR measurement light confined into a square of 160 μm.

When a mineral oil or a poly-α-olefin is used as the oily medium at thetime of preparing a sample, since such a material is a hydrocarbon,there is no characteristic absorption other than those of C—C and C—H.In consequence, since Illustrative Compound AII-1 in the sample has acarbonyl group of an ester bond exhibiting a distinct high-intensitycharacteristic absorption band, a change of the concentration can bequantitatively detected from the intensity of the characteristicabsorption band.

As a result of observation using the foregoing apparatus, it was notedthat in a so-called Hertzian area under a high pressure in a high shearfield, where a Newtonian ring is formed, Illustrative Compound II-1 wasgradually segregated in a form of a candle flame formed by partition ofa flow of the sample in, for example, a region of from 20 to 400 μmbackward.

FIG. 25 is a figure showing a portion wherein a Newtonian ring is formedupon point contact, a portion where a sample flows thereinto, and rightand left portions thereof.

FIG. 26 is an IR spectrum thereof. From the results shown in FIG. 26, itcan be understood that a stretching vibration band of a carbonyl groupat 1,750 cm⁻¹ and a stretching vibration band of ester C—O at 1,120 cm⁻¹increase with time.

In many cases, the concentration becomes substantially constant forabout 5 minutes to 2 hours under a condition at a measurementtemperature of 40° C. at a linear velocity of 0.15 m/sec under aHertzian pressure of 0.3 GPa, an aspect of which is, however, differentdepending upon a condition such as a temperature, etc.

FIG. 27 is a graph showing the temperature dependency of an absorbance.Obviously, it is noted that as a sample becomes close to a clearingpoint, namely a dispersion particle size of Illustrative Compound AII-1becomes small, a segregation rate of Illustrative Compound AII-1 alsobecomes small, a segregation amount of which is not more than ameasurement limit in this evaluation apparatus at a temperature of theclearing point or higher.

FIG. 28 is a graph showing a relation between a rotation speed of asteel ball, namely an amount at which a lubricating oil thereof is sentinto a point-contacting portion and a segregation amount. As expected,it can be understood from this graph that the higher the rotationnumber, namely the larger the amount of a dispersion composition sampleto be fed into the point-contacting portion, the more the segregationamount increases.

The foregoing point contact EHL evaluation apparatus is a model of theHertzian contact area under a high-pressure and high-shear condition,namely a true contact site. The actual friction contact area is an areawhere such true contact areas are crowded. Therefore, it may beconsidered that in a sample containing Illustrative Compound AII-1 inthe oily medium, the amount of the base oil with relatively lowviscosity (oily medium) becomes small in the vicinity of a number oftrue contact areas of such a friction contact area, whereby theforegoing Illustrative Compound AII-1 is accumulated.

In consequence, even when the amount of Illustrative Compound AII-1contained in the sample is small as about 1% by mass, and even under acondition under which there is a concern that originally, a compound isnot accumulated at a high temperature, it can be expected that if theconcentration of Illustrative Compound AII-1 is increased in the slidingportion, a low-viscosity effect is revealed under elastic fluidlubrication which is original to the subject compound even at the hightemperature, as indicated by the frictional coefficient at the hightemperature in an SRV evaluation apparatus.

7. Test Example 6

Performance Evaluation of Grease Composition:

Grease samples 1 to 5 each having a formulation shown in the followingtable were prepared using Illustrative Compounds AII-18, AI-64, AII-37,AI-71 and AIII-1, respectively. Moreover, comparative grease samples C1to C4 each having a formulation shown in the following table wereprepared, respectively.

A friction test was carried out, thereby measuring a coefficient offriction and a wear scar depth. In this connection, the coefficient offriction in the Examples was measured using a reciprocating frictiontester (SRV friction and wear tester), and the friction test was carriedout under the following test condition. The results of grease samples 1to 5 of the Examples are shown in the following Table 3, and the resultsof the comparative grease samples C1 to C4 are shown in the followingTable 4.

Test Condition:

The test condition was adopted by the ball-on-plate system.

Test piece (friction material): SUJ-2

Plate: φ24×6.9 mm

Ball: φ10 mm

Temperature: 70° C.

Load: 100 N

Aptitude: 1.0 mm

Frequency: 50 Hz

Test time: Measured 30 minutes after starting the test

TABLE 3 Grease Sample No. 1 2 3 4 5 Compound of the AII-18 AI-64 AII-37AI-71 AIII-1 Invention % by mass 3 5 3 5 3 Base Oil % by mass MineralOil *1 70 75 80 — — Poly-α-olefin *2 — — — 82 82 Thickener % by massLithium stearate 27 20 — — — Urea *3 — — 17 13 15 Mixed consistency (40288 265 274 251 299 degrees Celsius) Friction Coefficient 0.055 0.0850.060 0.084 0.069 Wear Depth (μm) 0.35 0.58 0.53 0.71 0.56 *1 Viscosity11 cst (100 degrees Celsius) *2 Viscosity 12 cst(100 degrees Celsius) *3Product obtained by reacting 1 equivalent amount of diphenyl methane4,4′-diisocyanate with 2 equivalent amounts of octadecyl amine.

TABLE 4 Grease Sample for Comparative Example No. C1 C2 C3 C4 Compoundof the Invention — — — — Base Oil % by mass Mineral Oil *1 75 — 85 —Poly-α-olefin *2 — 75 — 85 Thickener % by mass Lithium stearate 25 25 —— Urea *3 — — 15 15 Mixed consistency (40 degrees 320 317 311 307Celsius) Friction Coefficient 0.127 0.135 0.132 0.145 Wear Depth (μm)1.24 1.44 1.22 1.53 *1 Viscosity 11 cst (100 degrees Celsius) *2Viscosity 12 cst(100 degrees Celsius) *3 Product obtained by reacting 1equivalent amount of diphenyl methane 4,4′-diisocyanate with 2equivalent amounts of octadecyl amine.

From the results shown in the foregoing tables, it can be understoodthat the grease composition samples of the Examples containing thecompound of the invention conspicuously exhibit a friction reducingeffect and a wear inhibiting effect.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing the results of Test Example 1 of IllustrativeCompounds AII-1 and AII-2.

FIG. 2 is a graph showing the results of Test Example 1 of IllustrativeCompounds AII-17 and AII-18.

FIG. 3 is a graph showing the results of Test Example 1 of IllustrativeCompounds AII-65.

FIG. 4 is a graph showing the results of Test Example 1 of ComparativeCompounds C-1 and C-2.

FIG. 5 is a graph showing the results of Test Example 2 of thecompositions containing Illustrative Compounds AII-1 and AII-3,respectively.

FIG. 6 is a graph showing the results of Test Example 2 of thecompositions containing Illustrative Compounds AII-4 and AII-5,respectively.

FIG. 7 is a graph showing the results of Test Example 2 of thecompositions containing Illustrative Compounds AII-6 and AII-7,respectively.

FIG. 8 is a graph showing the results of Test Example 2 of thecompositions containing Illustrative Compounds AII-8 and AII-14,respectively.

FIG. 9 is a graph showing the results of Test Example 2 of thecompositions containing Illustrative Compounds AII-16 and AII-17,respectively.

FIG. 10 is a graph showing the results of Test Example 2 of thecompositions containing Illustrative Compounds AII-18 and AII-19,respectively.

FIG. 11 is a graph showing the results of Test Example 2 of thecompositions containing Illustrative Compounds AII-33 and AII-34,respectively.

FIG. 12 is a graph showing the results of Test Example 2 of thecompositions containing Illustrative Compounds AII-36 and AII-37,respectively.

FIG. 13 is a graph showing the results of Test Example 2 of thecompositions containing Illustrative Compounds AII-38 and AII-40,respectively.

FIG. 14 is a graph showing the results of Test Example 2 of thecompositions containing Illustrative Compounds AII-41 and AII-43,respectively.

FIG. 15 is a graph showing the results of Test Example 2 of thecomposition containing Illustrative Compounds AII-65.

FIG. 16 is a graph showing the results of Test Example 2 of thecomposition containing Illustrative Compounds AII-88 and AII-89,respectively.

FIG. 17 is a graph showing the results of Test Example 2 of thecomposition containing Illustrative Compounds AII-90.

FIG. 18 is a graph showing the results of Test Example 2 of thecompositions containing Comparative Compounds C-3 and C-6, respectively.

FIG. 19 is a graph showing the results of Test Example 2 of acommercially available mineral oil.

FIG. 20 is a graph showing the results of Text Example 3 of thecompositions prepared using Illustrative Compound AII-4 and acommercially available poly-α-olefin and a polyol ester, respectively.

FIG. 21 is a graph showing the results of Text Example 3 of thecompositions prepared using Illustrative Compound AII-4 and acommercially available ion fluid and N-methylpyrrolidone, respectively.

FIG. 22 is a graph showing the results of Test Example 4 of thecomposition containing Illustrative Compound AII-1.

FIG. 23 is a diagrammatic view of the apparatus used in Test Example 5.

FIG. 24 is a microscopic photograph of the Newtonian ring observed inTest Example 5.

FIG. 25 is a microscopic photograph of the Newtonian ring observed inTest Example 5.

FIG. 26 is an IR spectrum measured in Test Example 5.

FIG. 27 is a graph showing a fluctuation of an absorbance of an IRspectrum measured in Test Example 5 relative to a temperature change.

FIG. 28 is a graph showing a fluctuation of an absorbance of an IRspectrum measured in Test Example 5 relative to the rotation numberchange of a steel ball.

1. A compound represented by following formula (Z):A-L-{D¹-(E)_(q)-D²-(B)_(m)—Z¹—R}_(p)  (Z) wherein A is a grouprepresented by the following formula (A1) or (AIII);

wherein * means a bonding site to -L-D¹-(E)_(q)-D²-(B)^(m)—Z¹—R; Crepresents a carbon atom; R⁰ represents a hydrogen atom or asubstituent; each of X¹ to X⁴, X¹¹ to X¹⁴ and X²¹ to X²⁴ represents ahydrogen atom or a halogen atom and may be the same as or different fromevery other; each of n1 to n3 represents an integer of from 0 to 5; andm4 represents an integer of from 0 to 2; L represents a single bond, anoxy group, a substituted or non-substituted oxymethylene grouprepresented by following formula (A-a), or a substituted ornonsubstituted oxyethyleneoxy group represented by following formula(A-b):—(O—C(Alk)₂)-  (A-a)—(O—C(Alk)₂C(Alk)₂O)—  (A-b) Alk represents a hydrogen atom, a C₁-C₆alkyl group or a cycloalkyl group; p represents an integer of 3 or more;D¹ represents a carbonyl group (—C(═O)—) or a sulfonyl group (—S(═O)₂—),and each D¹ may be the same as or different from every other D¹; D²represents a carbonyl group (—C(═O)—), a sulfonyl group (—S(═O)₂—), acarboxyl group (—C(═O)O—), a sulfonyloxyl group (—S(═O)₂O—), a carbamoylgroup (—C(═O)N(Alk)-) or a sulfamoyl group (—S(═O)₂N(Alk)-), and each D²may be the same as or different from every other D², wherein Alkrepresents a hydrogen atom, a C₁-C₆ alkyl group or a cycloalkyl group; Erepresents a substituted or nonsubstituted alkylene group, cycloalkylenegroup, alkenylene group, alkynylene group or arylene group, a divalentheterocyclic aromatic ring group or heterocyclic non-aromatic ringgroup, a divalent group selected among an imino group, an alkyliminogroup, an oxy group, a sulfide group, a sulfenyl group, a sulfonylgroup, a phosphoryl group and an alkyl-substituted silyl group, or adivalent group composed of a combination of two or more of these groups;q represents an integer of 0 or more; and when q is 2 or more, each Emay be the same as or different from every other E; R represents ahydrogen atom, a substituted or non-substituted C₈ or longer alkylgroup, a perfluoroalkyl group or a trialkylsilyl group, and each R maybe the same as or different from every other R; B varies depending uponR; in the case where R represents a hydrogen atom or a substituted ornon-substituted C₈ or longer alkyl group, B represents a substituted ornon-substituted oxyethylene group or a substituted or non-substitutedoxypropylene group; plural Bs connecting to each other may be the sameas or different from each other; and m represents a natural number of 1or more; in the case where R represents a perfluoroalkyl group, Brepresents an oxyperfluoromethylene group, an oxyperfluoroethylene groupor an optionally branched oxyperfluoropropylene group; plural Bsconnecting to each other may be the same as or different from eachother; and m represents a natural number of 1 or more; in the case whereR represents a trialkylsilyl group, B represents a dialkylsiloxy groupin which the alkyl group is selected among a methyl group, an ethylgroup and an optionally branched propyl group; each B may be the same asor different from every other B; plural Bs connecting to each other maybe the same as or different from each other; and m represents a naturalnumber of 1 or more; and Z¹ represents a single bond, a divalent groupselected among a carbonyl group, a sulfonyl group, a phosphoryl group,an oxy group, a substituted or non-substituted amino group, a sulfidegroup, an alkenylene group, an alkynylene group and an arylene group ora divalent group composed of a combination of two or more of thesegroups.
 2. The compound according to claim 1, wherein in the formula(Z), each —(B)_(m)—Z¹—R is a group represented by following formula(ECa), and each —(B)_(m)—Z¹—R may be the same as or different from everyother —(B)_(m)—Z¹—R:

wherein in the formula (ECa), C represents a carbon atom; O representsan oxygen atom; R^(a) corresponding to R in the formula (Z) represents asubstituted or non-substituted C₈ or longer alkyl group; L^(a)corresponding to Z¹ in the formula (Z) represents a single bond or adivalent connecting group; each of X^(a1) and X^(a2) represents ahydrogen atom or a halogen atom; na1 represents an integer of from 1 to4; when na1 is 2 or more, plural X^(a1)s and X^(a2)s may be the same asor different from each other; and na2 represents a number of from 1 to35.
 3. The compound according to claim 2, wherein in formula (Z), L^(a)corresponding to Z¹ is a single bond or a divalent connecting groupcomposed of a combination of one or more members selected among acarbonyl group, a sulfonyl group, a phosphoryl group, an oxy group, asubstituted or non-substituted amino group, a thio group, an alkylenegroup, an alkenylene group, an alkynylene group and an arylene group. 4.The compound according to claim 1, wherein in formula (Z), each—(B)_(m)—Z¹—R is a group represented by following formula (ECb), andeach —(B)_(m)—Z¹—R may be the same as or different from every other—(B)_(m)—Z¹—R:

wherein in the formula (ECb), the same symbols as those in the formula(ECa) according to claim 4 are synonymous, respectively; L^(a1)corresponding to Z¹ in the formula (Z) represents a single bond; na2represents a number of from 0 to 2; nc represents a number of from 1 to10; m represents a number of from 1 to 12; and n represents a number offrom 1 to
 3. 5. The compound according to claim 1, wherein in formula(Z), each —(B)_(m)—Z¹—R is a group represented by following formula(ECc), and each —(B)_(m)—Z¹—R may be the same as or different from everyother —(B)_(m)—Z¹—R:

wherein in formula (ECc), the same symbols as those in formula (ECa)according to claim 4 are synonymous, respectively; each Alk′ may be thesame as or different from every other Alk′ and represents a C₁-C₄ alkylgroup; L^(a1) corresponding to Z¹ in the formula (Z) represents a singlebond; and nb represents a number of from 1 to 10.